Seven 3-methylidene-1H-indol-2(3H)-ones related to the multiple-receptor tyrosine kinase inhibitor sunitinib

The solid-state structures of a series of seven substituted 3-methylidene-1H-indol-2(3H)-one derivatives have been determined by single-crystal X-ray diffraction and are compared in detail. Six of the structures {(3Z)-3-(1H-pyrrol-2- ylmethylidene)-1H-indol-2(3H)-one, C13H10N2O, (2a); (3Z)-3-( 2-thienylmethylidene)-1H-indol-2(3H)-one, C13H9NOS, (2b); (3E)-3-(2-furylmethylidene)-1H-indol-2(3H)-one monohydrate, C13H9NO2 center dot H2O, (3a); 3-(1-methylethylidene)-1H-indol- 2(3H)-one, C11H11NO, (4a); 3-cyclohexylidene-1H-indol- 2(3H)-one, C14H15NO, (4c); and spiro[1,3-dioxane-2,3'-indolin]- 2'-one, C11H11NO3, (5)} display, as expected, intermolecular hydrogen bonding (N-H center dot center dot center dot O=C) between the 1H-indol-2(3H)-one units. However, methyl 3-(1-methylethylidene)- 2-oxo-2,3-dihydro-1H-indole-1-carboxylate, C13H13NO3, (4b), a carbamate analogue of (4a) lacking an N-H bond, displays no intermolecular hydrogen bonding. The structure of (4a) contains three molecules in the asymmetric unit, while (4b) and (4c) both contain two independent molecules.

C-H activations on a 1H-1,4-benzodiazepin-2(3H)-one template

Air stable benzodiazepine containing palladacycles were synthesized by a C-H activation reaction and studied by mass spectrometry and X-ray crystallography. Catalytic C-H functionalizations of 1-methyl-5-phenyl-1H-1,4-benzodiazepin-2(3H)-one with diphenyliodonium hexafluorophosphate led to a mixture, which included the starting material and the expected product 1-methyl-5-(2'-biphenyl)-1H-1,4-benzodiazepin-2(3H)-one. (C) 2008 Elsevier Ltd. All rights reserved.

Achiral, selective CCK2 receptor antagonists based on a 1,3,5-benzotriazepine-2,4-dione template

Novel, achiral 1H-1,3,5-benzotriazepine-2,4(3H,5H)-diones have been prepared and structurally characterized. These compounds are potent CCK2 receptor antagonists that display a high degree of selectivity over CCK1 receptors.

Microwave mediated reduction of heterocycle and fluorine containing nitroaromatics with Mo(CO)(6) and DBU

Heterocycle containing nitroaromatics were reduced by Mo(CO)(6) and DBU in EtOH under microwave irradiation within 15 min. Under the same conditions, 4-fluoronitrobenzene was reduced to 4-fluoroaniline, whereas 2-chloro-1-fluoro-4-nitrobenzene afforded a mixture of 3-chloro-4-fluoroaniline and 3-chloro-4-ethoxyaniline. The extent of the competing SNAr/reduction process could be influenced by the nature of the solvent, with t-BuOH the inert solvent of choice. The latter was used as solvent for SNAr/reductions of 2-chloro-1-fluoro-4-nitrobenzene with S-nucleophiles to yield 3-chloro-4-mercaptoanilines. Crown Copyright (c) 2008 Published by Elsevier Ltd. All rights reserved.

C-H activations via palladacycles

Summary: This chapter contains sections titled: * Introduction: CC Bond Formation via Cyclopalladation Reactions * Stoichiometric CH Activation Chemistry * Catalytic Chemistry * Arylations * Direct CH CH Coupling Reactions * Alkylations * Other Reactions * Conclusion * References

Adult personality inconsistency and problems with parents: uncovering the roots of the false self

Research has established that individuals who tend to vary their personality depending on who they are with, show a variety of signs of psychological maladjustment in comparison to those who do not; they show more negative affect (Baird, Le and Lucas, 2006), lower life satisfaction (Suh, 2002), lower self-esteem (Sheldon et al., 1997), lower role-satisfaction (Donahue et al., 1993), higher rates of depression (Lutz and Ross, 2003), more anxiety (Diehl, Hastings and Stanton, 2001) and poorer physical health (Cross, Gore and Morris, 2003). It has also been shown that personality variability is positively related to the experience of inauthenticity and falsity (Sheldon et al., 1997). Donahue, Roberts, Robins and John (1993) found that personality inconsistency of this type is related to tension within the family. Psychoanalytic theory has also linked the operation of an adult false self to experiences with parents, particularly in early life (Winnicott, 1960). It was hypothesized that personality variability and the adult experience of falsity in social situations would be related to an emotionally unstable relationship with parents. The method to test this comprised a questionnaire-based survey given to a non-clinical population. The final sample comprised 305, with 193 women and 112 men, aged from 19 to 55. The first questionnaire asked participants to rate personality traits, including emotional stability, in three social contexts - with parents, with friends and with work colleagues. The second part involved 3 questions; participants were asked to select in which of the aforementioned three social contexts they felt “most themselves”; in which they were “most authentic” and in which they “put on a front”. It was found, consistent with predictions, that an index of overall personality variability calculated from the personality questionnaire correlated strongly with emotional instability around parents (r = 0.46, p<0.001), while not correlating with emotional instability in either of the other two contexts measured. This suggests a specific link between a person’s relationship with their parents and their overall personality integration. Furthermore, it was found that participants who cited one of the three social contexts (parents, friends, work colleagues) as being one in which they were “more themselves” or “more authentic” had significantly higher ratings of emotional instability with parents than those participants who found that they were equally authentic across settings (F = 9.8, p<0.005). The results suggest a clear link between a person’s relationships with their parents and their adult personality integration. An explanation is that individuals who experience an anxious or ambiguous attachment with their parents in childhood may fear rejection or abandonment in later life, and so habitually adapt their personality to fit in to social contexts as adults, in order to be accepted by others and to minimize the possibility of social rejection. These individuals meanwhile retain an emotionally unstable relationship with their parents in adulthood. This interpretation is speculative but is open to empirical testing. Clinicians should be aware that attachment problems with parents may underlie poor personality integration in adulthood.

Individual crisis episodes and cultural transition: finding the macrocosm in the microcosm

According to dialogical self theory (Hermans, 2001), individual identities reflect cultural and subcultural values, and appropriate voices and discourses from the social environment. Bronfenbrenner’s (1979) systemic theory of human development similarly postulates that individual and social development occur in a symbiotic and interdependent fashion. It would therefore be predicted that individual changes in identity reflect macrocosmic changes in cultural values and social structures. The current study investigated narratives of crisis transitions within adults aged 25-40, by way of interviews with 22 participants. An intensive qualitative analysis showed that the narratives of crisis could indeed be viewed as individual manifestations of contemporary cultural changes. National statistics and academic research have documented in the UK substantial cultural shifts over the last twenty years including the lessening popularity of marriage, the rise of freelance and portfolio careers and the growth of accepted alternative gender roles. In individual crises, changes made over the course of the episode were invariably in the same direction as these social changes; towards flexible work patterns, non-marital relationships and redefined gender identities. Before the crisis, participants described their identity as bound into an established discourse of conventionality, a traditional sense of masculinity or feminitity and a singular career role, while after the crisis alternative and fluid identities are explored, and identity is less defined by role and institution. These findings show that changes in the social macrocosm can be found in the individual microcosm, and therefore support dialogical self theory.

Other uses of palladacycles in synthesis

Summary: This chapter contains sections titled: * Introduction * Chiral Palladacycles in Aldol and Related Transformations * Catalytic Allylic Rearrangements * Catalytic C-C Bond-Forming Reactions * Oxidations Involving Palladacycles * Conclusion * References

Sediment transfer and accumulation in two contrasting salt marsh/mudflat systems: the Seine estuary (France) and the Medway estuary (UK)

Understanding the dynamics of fine sediment transport across the upper intertidal zone is critical in managing the erosion and accretion of intertidal areas, and in managed realignment/estuarine habitat recreation strategies. This paper examines the transfer of sediments between salt marsh and mudflat environments in two contrasting macrotidal estuaries: the Seine (France) and the Medway (UK), using data collected during two joint field seasons undertaken by the Anglo-French RIMEW project (Rives-Manche Estuary Watch). High-resolution ADCP, Altimeter, OBS and ASM measurements from mudflat and marsh surface environments have been combined with sediment trap data to examine short-term sediment transport processes under spring tide and storm flow conditions. In addition, the longer-term accumulation of sediment in each salt marsh system has been examined via radiometric dating of sediment cores. In the Seine, rapid sediment accumulation and expansion of salt marsh areas, and subsequent loss of open intertidal mudflats, is a major problem, and the data collected here indicate a distinct net landward flux of sediments into the marsh interior. Suspended sediment fluxes are much higher than in the Medway estuary (averaging 0.09 g/m(3)/s), and vertical accumulation rates at the salt marsh/mudflat boundary exceed 3 cm/y. Suspended sediment data collected during storm surge conditions indicate that significant in-wash of fine sediments into the marsh interior can occur during (and following) these high-magnitude events. In contrast to the Seine, the Medway is undergoing erosion and general loss of salt marsh areas. Suspended sediment fluxes are of the order of 0.03 g/m(3)/s, and the marsh system here has much lower rates of vertical accretion (sediment accumulation rates are ca. 4 mm/y). Current velocity data for the Medway site indicate higher velocities on the ebb tide than occur on the flood tide, which may be sufficient to remobilise sediments deposited on the previous tide and so force net removal of material from the marsh.

Organometallic pincer-type complexes: recent applications in synthesis and catalysis

YCY pincer palladacycles, where YCY is typically an SCS, NCN, PCP, SeCSe anionic six-electron donor ligand (e.g. see 1-6, Scheme 1.1), are a well-established family of organometallic complexes with manifold applications in catalysis, synthesis and materials science [1-24]. Their synthesis can be achieved by many routes including C-H activation, oxidative addition, transmetalation and trans-cyclopalladation [25].

Synthesis of cycloruthenated compounds as potential anticancer agents

A library of 19 cycloruthenated derivatives is constructed by making use of the well-known cyclometalation reaction. Their geometries are modified in a straightforward manner by addition of either mono- or bidentate ligands, such as bipyridine, phenanthroline, 1,2-bis(diphenylphosphanyl)ethane, dimethylphenylphosphane, triphenylphosphane, and 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane (PTA) ligands, to cationic cycloruthenated centers. The antitumor properties of the compounds thus obtained are investigated in order to compare them with recently reported ruthenium complexes and cisplatin. IC50 values against mammalian cells (A-172, HCT-116, and RDM-4) are determined for the library compounds and some of them, such as those derived from orthoruthenated phenylpyridine and a bidentate N,N ligand, display activity of the same order of magnitude as cisplatin.