A new chiral oxazoline derived from camphor and its conversion to (R)-2-methylalkanoic acids

1S,5R,7R)-(-)-10, 10-Dimethyl-3-ethyl-4-oxa--atricyclo[5.2.1.0(1,5)]dec-2-ene 2 was prepared in 95% yield from (1S)-1-amino-2-exo-hydroxyapocamphane 1. The chiral oxazoline could be alkylated (Lhttp://eprints.iisc.ernet.in/cgi/users/home?screen=EPrint::Edit&eprintid=31175&stage=core#tDA/THF/-78 degrees C/RX, RX = ethyl, n-propyl, n-butyl iodides or benzyl bromide) to 3 in 95% yield and > 95% diastereoselectivity, and the products hydrolysed to (R)-2-methylalkanoic acids 4 (43-47% yield, 93-98% e.e.). (C) 2000 Elsevier Science Ltd. All rights reserved.

Crystal structure and conformation study of N-methyl-t-3-methyl-r-2, c-6-diphenylpiperidin-4-one thiosemicarbazone

Thiosemicarbazones are having the ability to bind with metal and inhibit the enzyme ribonucleoside diphosphate reductase(RDR),an enzyme which is involved in the synthesis of DNA precursors in the mammalian cells.The title compound N-methyl-t-3-methyl-r-2, c-6-diphenylpiperidin-4-one thiosemicarbazone (NMMDPT), CCDC 218052, was prepared using Mannich reaction and characterized by X-ray diffraction methods.The crystal data are:C20H24N4S; M.W= 352.49, triclinic,space group P (1) over bar, a = 8.467(2)angstrom, b = 10.228(2)angstrom, c = 12.249(2)angstrom; lpha=92.595(3)degrees, beta=104.173(3)degrees, gamma=13.628(3)degrees; V=930.0(3)angstrom(3), Z=2, D-cal=1.259Mgm(-3),mu=0.184mm(-1),lambda (MoKalpha)=0.71073 angstrom, final R1 and wR2 are 0.0470 and 0.1052, respectively. The piperidine rings adopt chair conformation. The planar phenyl rings are oriented equatorially at 2,6-positions of the piperidine ring. The molecular packing can be viewed as dimers held together by two N-H...S types of intermolecular hydrogen bonds. Weak C-H...pi interactions also support the stability of the molecules in the crystal in addition to van der Waals forces. (c) 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure of N-nitroso-r-2,c-7-diphenylhexahydro-1,4-diazepin-5-one

C17H17N3O2, M(r) = 295.34, orthorhombic, P2(1)2(1)2(1), a = 7.659 (1), b = 12.741 (1), c = 15.095 (1) angstrom, V = 1473.19 (2) angstrom 3, Z = 4, D(m) = 1.33, D(x) = 1.32 Mg m-3, lambda(Cu K-alpha) = 1.5418 angstrom, mu = 0.68 mm-1, F(000) = 624, T = 295 K, R = 0.031 for 1549 unique observed reflections with I > 2.5-sigma(I). The seven-membered heterocyclic ring adopts a boat conformation flattened at the nitroso end of the ring. The substituent phenyl rings occupy pseudo-axial positions and the nitroso group is coplanar with the C(2), N(1), C(7) plane of the central ring. The crystal structure is stabilized by intermolecular N-H...O and weak C-H...O hydrogen bonds.

Structure and Bonding in Stannadiphospholes and their Dianions SnC(2)P(2)R(2)(m) (R=H, tBu m=0,-2): A Comparative Study with C(5)H(5)(+) and C(5)H(5)(-) Analogues

The potential energy surfaces of both neutral and dianionic SnC(2)P(2)R(2) (R=H, tBu) ring systems have been explored at the B3PW91/LANL2DZ (Sn) and 6-311 + G* (other atoms) level. In the neutral isomers the global minimum is a nido structure in which a 1,2-diphosphocyclobutadiene ring (1,2-DPCB) is capped by the Sn. Interestingly, the structure established by Xray diffraction analysis, for R=tBu, is a 1,3-DPCB ring capped by Sn and it is 2.4 kcal mol(-1) higher in energy than the 1,2-DPCB ring isomer. This is possibly related to the kinetic stability of the 1,3-DPCB ring, which might originate from the synthetic precursor ZrCp(2)tBu(2)C(2)P(2). In the case of the dianionic isomers we observe only a 6 pi-electron aromatic structure as the global minimum, similarly to the cases of our previously reported results with other types of heterodiphospholes.([1,4,19]) The existence of large numbers of cluster-type isomers in neutral and 6 pi-planar structures in the dianions SnC(2)P(2)R(2)(2-) (R=H, tBu) is due to 3D aromaticity in neutral clusters and to 2D pi aromaticity of the dianionic rings. Relative energies of positional isomers mainly depend on: 1) the valency and coordination number of the Sn centre, 2) individual bond strengths, and 3) the steric effect of tBu groups. A comparison of neutral stannadiphospholes with other structurally related C(5)H(5)(+) analogues indicates that Sn might be a better isolobal analogue to P(+) than to BH or CH(+). The variation in global minima in these C(5)H(5)(+) analogues is due to characteristic features such as 1) the different valencies of C, B, P and Sn, 2) the electron deficiency of B, 3) weaker p pi-p pi bonding by P and Sn atoms, and 4) the tendency of electropositive elements to donate electrons to nido clusters. Unlike the C5H5+ systems, all C(5)H(5)(-) analogues have 6 pi-planar aromatic structures as global minima. The differences in the relative ordering of the positional isomers and ligating properties are significant and depend on 1) the nature of the pi orbitals involved, and 2) effective overlap of orbitals.

Digestive ripening and green synthesis of ultra-small (r < 2 nm) stable ZnO quantum dots

Given the recent reports pertaining to novel optical properties of ultra-small quantum dots (QDs) (r <2 nm), this nanomaterial is of relevance to both technology and science. However it is well known that in these size regimes most chalocogenide QD dispersions are unstable. Since applications often require use of QD dispersions (e.g. for deployment on a substrate), stabilizing these ultra-small particles is of practical relevance. In this work we demonstrate a facile, green, solution approach for synthesis of stable, ultra-small ZnO QDs having radius less than 2 nm. The particle size is calculated using Brits' equation and confirmed by transmission electron micrographs. ZnO QDs reported remain stable for > 120 days in ethanol (at similar to 298-303 K). We report digestive ripening (DR) in TEA capped ZnO QDs; this occurs rapidly over a short duration of 5 min. To explain this observation we propose a suitable mechanism based on the Lee's theory, which correlates the tendency of DR with the observed zeta potentials of the dispersed medium. To the best of our knowledge this is the (i) first report on DR in oxide QDs, as well as the first direct experimental verification of Lee's theory, and (ii) most rapid DR reported so far. The facile nature of the method presented here makes ultra-small ZnO readily accessible for fundamental exploration and technologically relevant applications. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Ethyl 6-chloro-2-oxo-4-phenyl-1,2-dihydroquinoline-3-carboxylate

In the title compound,C18H14ClNO3,the dihydroquinolin-2-one ring system is almost planar (r.m.s.deviation = 0.033 angstrom).The carboxylate plane and the phenyl group are twisted away from the dihydroquinolin-2-one ring system by 50.3(1) and 64.9(1)degrees,respectively.In the crystal structure, inversion-related molecules form R-2(2)(8)dimers via pairs of N-H center dot center dot center dot O hydrogen bonds.

3-[(2-Chloro-6-methylquinolin-3-yl)methyl]quinazolin-4(3H)-one

In the title molecule, C19H14ClN3O, the quinoline and quinazoline ring systems form a dihedral angle of 80.75 (4)degrees. In the crystal, the molecules are linked by pairs of C-H center dot center dot center dot N hydrogen bonds into centrosymmetric dimers, generating R-2(2)(6) ring motifs. The structure is further stabilized by C-H center dot center dot center dot pi interactions and pi-pi stacking interactions [centroid-centroid distances = 3.7869 (8) and 3.8490 (8) angstrom].

4-Azidomethyl-7-methyl-2-oxo-2H-chromene-6-sulfonyl azide

In the title compound, C11H8N6O4S, the plane of the coumarin aromatic ring is twisted by 17.2 (2)degrees with respect to the plane of the azide group bound to the methylene substituent, whereas it is twisted by 83.2 (2)degrees to the plane of the azide attached to the sulfonyl group. The crystal structure is stabilized by weak C-H center dot center dot center dot O interactions, leading to the formation of dimers with R-2(2)(12) graph-set motifs. These dimers are further linked by weak S-O center dot center dot center dot pi and pi-pi contacts centroid-centroid distance = 3.765 (2) angstrom], leading to the formation of a layered structure.

Synthesis, Reactivity, Structural Aspects, and Solution Dynamics of Cyclopalladated Compounds of N,N `,N `'-Tris(2-anisyl)guanidine

N,N',N `'-Tris(2-anisyl)guanidine, (ArNH)(2)C=NAr (Ar = 2-(MeO)C6H4), was cyclopallaclated with Pd(OC(O)R)(2) (R = Me, CF3) in toluene at 70 degrees C to afford palladacycles Pd{kappa(2)(C,N)-C6H3-(OMe)-3(NHC(NHAr)(=NAr))-2}(mu-OC(O)R)](2)(R = Me (1a) and CF3 (1b)) in 87% and 95% yield, respectively. Palladacycle 1a was subjected to a metathetical reaction with LiBr in aqueous ethanol at 78 degrees C to afford palladacycle Pd{kappa(2)(C,N)-C6H3(OMe)-3(NHC(NHAr)(=NAr))-2}(mu-Br)](2) (2) in 90% yield. Palladacycle 2 was subjected to a bridge-splitting reaction with Lewis bases in CH2Cl2 to afford the monomeric palladacycles Pd{kappa(2)(C,N)-C6H3(OMe)-3(NHC(NHAr)(=NAr))-2}Br(L)] (L = 2,6-Me2C5H3N (3a), 2,4-Me2C5H3N (3b), 3,5-Me2C5H3N (3c), XyNC (Xy = 2,6-Me2C6H3; 4a), (BuNC)-Bu-t (4b), and PPh3 (5)) in 87-95% yield. Palladacycle 2 upon reaction with 2 equiv of XyNC in CH2Cl2 afforded an unanticipated palladacycle, Pd{kappa(2)(C,N)-C(=NXy)(C6H3(OMe)-4)-2(N=C-(NH Ar)(2))-3} Br(CNXy)] (6) in 93% yield, and the driving force for the formation of 6 was ascribed to a ring contraction followed by amine-imine tautomerization. Palladacycles 1 a,b revealed a dimeric transoid in-in conformation with ``open book'' framework in the solid state. In solution, 1 a exhibited a fluxional behavior ascribed to the six-membered ``(C,N)Pd'' ring inversion and partly dissociates to the pincer type and kappa(2)-O,O'-OAc monomeric palladacycles by an anchimerically assisted acetate cleavage process as studied by variable-temperature H-1 NMR data. Palladacycles 3a,b revealed a unique trans configuration around the palladium with lutidine being placed trans to the Pd-C bond, whereas cis stereochemistry was observed between the Pd-C bond and the Lewis base in 4a (as determined by X-ray diffraction data) and 5 (as determined by P-31 and C-13 NMR data). The aforementioned stereochemical difference was explained by invoking relative hardness/softness of the donor atoms around the palladium center. In solution, palladacycles 3a-c exist as a mixture of two interconverting boat conformers via a planar intermediate without any bond breaking due to the six-membered ``(C,N)Pd'' ring inversion, whereas palladacycles 4a,b and 5 exist as a single isomer, as deduced from detailed H-1 NMR studies.

Oxidative addition of tetrachloro-1,2-benzoquinone to lambda(3)-cyclotriphosphazanes. An unusual ring contraction-rearrangement

The lambda(3)-cyclotriphosphazanes, [EtNP(OR)](3) [R = 2,6-Me2C6H3 (1), 4-BrC6H4 (2), or CH2CF3(3)], on treatment with tetrachloro-1,2-benzoquinone (TCB) give the lambda(5)-cyclodiphosphazanes, [EtNP(O2C6Cl4)(OR)][EtNP(O2C6Cl4){N(Et)P(OR)(2)}] (5-7) by an unusual ring contraction-rearrangement. The reaction of the mixed substituent lambda(3)-cyclotriphosphazane, [(EtN)(3)P-3(OR)(2)(OR')] [R = 2,6-Me2C6H3, R' = 4-BrC6H4] (4), with TCB gives the lambda(5)-cyclodiphosphazane, [EtNP(O2C6Cl4)(OR')][EtNP(O2C6Cl4){N(Et)P(OR)(2)}] (8), in which 4-bromophenoxide resides on one of the ring phosphorus atoms. The lambda(3)-bicyclic tetraphosphapentazane, (EtN)(5)P-4(OPh)(2), on treatment with TCB undergoes a double ring contraction-rearrangement to give the lambda(5)-cyclodiphosphazane, (EtN)[(EtN)(2)P-2(O2C6Cl4)(2)(OPh)](2) (9). Variable-temperature and high-field P-31 NMR studies indicate the presence of more than one isomer in solution for the rearranged products 5-9. The solid state structure of 8 reveals a trans arrangement of the substituents with respect to the P2N2 ring in contrast to the gauche arrangement observed for 5.

Computational Study of the Formation of Short Centrosymmetric N-center dot center dot center dot S Supramolecular Synthon and Related Weak Interactions in Crystalline 1,2,4-Triazoles

A comprehensive analysis of the crystal packing and the energetic features of a series of four biologically active molecules belonging to the family of substituted 4-(benzylideneamino)-3-(4-fluoro-3-phenoxyphenyl)-1H-1,2,4-triazole-5-(4 H)-thione derivatives have been performed based on the molecular conformation and the supramolecular packing. This involves the formation of a short centrosymmetric R-2(2)(8) NH...S supramolecular synthon in the solid state, including the presence of CH...S, CH...O, CH...N, CH...F, CH...Cl, CF...FC, CCl...ClC, and CH...pi intermolecular interactions along with pp stacking to evaluate the role of noncovalent interactions in the crystal. The presence of such synthons has a substantial contribution toward the interaction energy (-18 to -20 kcal/mol) as obtained from the PIXEL calculation, wherein the Coulombic and polarization contribution are more significant than the dispersion contribution. The geometrical characteristics of such synthons favor short distance, and the population of related molecules having these geometries is rare as has been obtained from the Cambridge Structural Database (CSD). Furthermore, their interaction energies have been compared with those present in our molecules in the solid state. The topological characteristics of the NH...S supramolecular synthon, in addition to related weak interactions, CH...N, CH...Cl, CF...FC, and CCl...ClC, have been estimated using the quantum theory of atoms in molecules (QTAIM). In addition, an analysis of the Hirshfeld surface and associated fingerprint plots of these four molecules also have provided a platform for the evaluation of the contribution of different atom...atom contacts, which contribute toward the packing of the molecules in solids.

Morphological and functional characterisation of the burrow systems of six earthworm species (Lumbricidae)

Earthworm burrow systems are generally described based on postulated behaviours associated with the three ecological types. In this study, we used X-ray tomography to obtain 3D information on the burrowing behaviour of six very common anecic (Aporrectodea nocturna and Lumbricus terrestris) and endogeic (Aporrectodea rosea, Allolobophora chlorotica, Aporrectodea caliginosa, Aporrectodea icterica) earthworm species, introduced into repacked soil cores for 6 weeks. A simple water infiltration test, the Beerkan method, was also used to assess some functional properties of these burrow systems. Endogeic worms make larger burrow systems, which are more highly branched, less continuous and of smaller diameter, than those of anecic worms. Among the anecic species, L. terrestris burrow systems are shorter (9.2 vs 21.2 m) with a higher number (14.5 vs 23.5) of less branched burrows (12.2 vs 20.2 branches m(-1)), which are also wider (7.78 vs 5.16 mm) than those of A. nocturna. In comparison, the burrow systems made by endogeic species appeared similar to each other. However, A. rosea burrows were short and narrow, whereas A. icterica had a longer burrow system (15.7 m), more intense bioturbation intensity (refilled macropores or soil lateral compaction around them) and thus a greater number of burrows. Regarding water infiltration, anecic burrow systems were far more efficient due to open burrows linking the top and bottom of the cores. For endogeic species, we observed a linear relationship between burrow length and the water infiltration rate (R (2) = 0.49, p < 0.01). Overall, the three main characteristics significantly influencing water infiltration were burrow length, burrow number and bioturbation volume. This last characteristic highlighted the effect of burrow refilling by casts.

Non-linear regression model for spatial variation in precipitation chemistry for South India

Chemical composition of rainwater changes from sea to inland under the influence of several major factors - topographic location of area, its distance from sea, annual rainfall. A model is developed here to quantify the variation in precipitation chemistry under the influence of inland distance and rainfall amount. Various sites in India categorized as 'urban', 'suburban' and 'rural' have been considered for model development. pH, HCO3, NO3 and Mg do not change much from coast to inland while, SO4 and Ca change is subjected to local emissions. Cl and Na originate solely from sea salinity and are the chemistry parameters in the model. Non-linear multiple regressions performed for the various categories revealed that both rainfall amount and precipitation chemistry obeyed a power law reduction with distance from sea. Cl and Na decrease rapidly for the first 100 km distance from sea, then decrease marginally for the next 100 km, and later stabilize. Regression parameters estimated for different cases were found to be consistent (R-2 similar to 0.8). Variation in one of the parameters accounted for urbanization. Model was validated using data points from the southern peninsular region of the country. Estimates are found to be within 99.9% confidence interval. Finally, this relationship between the three parameters - rainfall amount, coastline distance, and concentration (in terms of Cl and Na) was validated with experiments conducted in a small experimental watershed in the south-west India. Chemistry estimated using the model was in good correlation with observed values with a relative error of similar to 5%. Monthly variation in the chemistry is predicted from a downscaling model and then compared with the observed data. Hence, the model developed for rain chemistry is useful in estimating the concentrations at different spatio-temporal scales and is especially applicable for south-west region of India. (C) 2008 Elsevier Ltd. All rights reserved.

On the cubicity of bipartite graphs

A unit cube in k-dimension (or a k-cube) is defined as the Cartesian product R-1 x R-2 x ... x R-k, where each R-i is a closed interval on the real line of the form [a(j), a(i), + 1]. The cubicity of G, denoted as cub(G), is the minimum k such that G is the intersection graph of a collection of k-cubes. Many NP-complete graph problems can be solved efficiently or have good approximation ratios in graphs of low cubicity. In most of these cases the first step is to get a low dimensional cube representation of the given graph. It is known that for graph G, cub(G) <= left perpendicular2n/3right perpendicular. Recently it has been shown that for a graph G, cub(G) >= 4(Delta + 1) In n, where n and Delta are the number of vertices and maximum degree of G, respectively. In this paper, we show that for a bipartite graph G = (A boolean OR B, E) with |A| = n(1), |B| = n2, n(1) <= n(2), and Delta' = min {Delta(A),Delta(B)}, where Delta(A) = max(a is an element of A)d(a) and Delta(B) = max(b is an element of B) d(b), d(a) and d(b) being the degree of a and b in G, respectively , cub(G) <= 2(Delta' + 2) bar left rightln n(2)bar left arrow. We also give an efficient randomized algorithm to construct the cube representation of G in 3 (Delta' + 2) bar right arrowIn n(2)bar left arrow dimension. The reader may note that in general Delta' can be much smaller than Delta.

An upper bound for Cubicity in terms of Boxicity

An axis-parallel b-dimensional box is a Cartesian product R-1 x R-2 x ... x R-b where each R-i (for 1 <= i <= b) is a closed interval of the form [a(i), b(i)] on the real line. The boxicity of any graph G, box(G) is the minimum positive integer b such that G can be represented as the intersection graph of axis-parallel b-dimensional boxes. A b-dimensional cube is a Cartesian product R-1 x R-2 x ... x R-b, where each R-i (for 1 <= i <= b) is a closed interval of the form [a(i), a(i) + 1] on the real line. When the boxes are restricted to be axis-parallel cubes in b-dimension, the minimum dimension b required to represent the graph is called the cubicity of the graph (denoted by cub(G)). In this paper we prove that cub(G) <= inverted right perpendicularlog(2) ninverted left perpendicular box(G), where n is the number of vertices in the graph. We also show that this upper bound is tight.Some immediate consequences of the above result are listed below: 1. Planar graphs have cubicity at most 3inverted right perpendicularlog(2) ninvereted left perpendicular.2. Outer planar graphs have cubicity at most 2inverted right perpendicularlog(2) ninverted left perpendicular.3. Any graph of treewidth tw has cubicity at most (tw + 2) inverted right perpendicularlog(2) ninverted left perpendicular. Thus, chordal graphs have cubicity at most (omega + 1) inverted right erpendicularlog(2) ninverted left perpendicular and circular arc graphs have cubicity at most (2 omega + 1)inverted right perpendicularlog(2) ninverted left perpendicular, where omega is the clique number.