Base- and light-assisted synthesis of anthracenes from 3-allylnaphthalene-2-carbaldehydes

The synthesis of substituted anthracenes from naphthalene precursors is described. The key step involved heating ortho-allyl substituted naphthalene-2-carbaldehydes and potassium t-butoxide in DMF with concomitant irradiation from a high pressure mercury lamp to afford anthracenes in yields of 76-98%.     

Cisplatin-DNA cross-link retro models with a chirality-neutral carrier ligand: evidence for the importance of "second-sphere communication"

We employ retro models, cis-PtA2G2 (A2 = a diamine, G = guanine derivative), to assess the cross-linked head-to-head (HH) form of the cisplatin-DNA d(GpG) adduct widely postulated to be responsible for the anticancer activity. Retro models are designed to have minimal dynamic motion to overcome problems recognized in models derived from cisplatin [A2 = (NH3)2]; the latter models are difficult to understand due to rapid rotation of G bases about the Pt-N7 bond in solution and the dominance of the head-to-tail (HT) form in the solid. Observation of an HH form is unusual for cis-PtA2G2 models. Recently, we found the first HH forms for a cis-PtA2G2 model with A2 lacking NH groups in a study of new Me2ppzPtG2 models. (Me2ppz, N,N'-dimethylpiperazine, has inplane bulk which reduces dynamic motion by clashing with the G O6 as the base rotates into the coordination plane from the ground state position approximately perpendicular to this plane G = 5'-GMP and 3'-GMP.) The finding of an HH form (albeit in a mixture with HT forms) with both G H8 signals unusually downfield encouraged us to study additional Me2ppzPtG2 analogues in order to explain the unusual spectral features and to identify factors that influence the relative stability of HT and HH forms. Molecular modeling techniques suggest HH structures with the H8's close to the deshielding region of the z axis of the magnetically anisotropic Pt atom, explaining the atypical shift pattern. When G = 1-Me-5'-GMP, we obtained NMR evidence that the HH rotamer has a high abundance (34%) and that the three rotamers have nearly equal abundance. These findings and the observation that the relative HT distributions varied little or not at all as a function of pH when G = Guo, 1-MeGuo, or 1-Me-5'-GMP are consistent with two of our earlier proposals concerning phosphate groups in HT forms of cis-PtA2(GMP)2 complexes. We proposed that a G phosphate group can form hydrogen bonds with the cis G N1H ("second-sphere" communication) and (for 5'-phosphate) A2 NH groups. The new results with 1-Me-5'-GMP led us to propose a new role for a 5'-phosphate group; it can also favor the HH form by counteracting the natural preference for the G bases to adopt an HT orientation. Finally, the HH form was also sufficiently abundant to allow observation of a distinct 195Pt NMR signal (downfield of the resonance observed for the HT forms) for several complexes. This is the first report of an HH 195Pt NMR signal for cis-PtA2G2 complexes.     

Pyrolysis-mass spectrometry correlations of crosslink density in natural rubber vulcanizates

A set of twelve natural rubber vulcanizates was analyzed by Curie-point pyrolysis-mass spectrometry (Py-MS). Multivariate analysis successfully correlated the Py-MS data with either total or polysulfidic crosslink density measurements. (Polysulfidic means two or more sulfurs.) The principal correlation observed was an increase in the ratio of monomer to dimer pyrolyzate yield with an increase in crosslink density. The feasibility of using Py-MS for total crosslink density determination has thus been demonstrated. The Py-MS data, however, did not allow us to distinguish different types of crosslinks.     

Two-Color Two-Photon Excitation of Fluorescence

Abstract— We report the observation of two-photon excitation of an organic fluorophore with two different wavelengths, a phenomenon we refer to as two-color two-photon (2C2P) excitation. Ultraviolet emission of p -Merphenyl at 340 nm was observed when the sample was illuminated with both 375 and 750 nm pulses from a picosecond dye laser. The emission of p -terphenyl was about 100-fold and more than 1000-fold less for illumination at only 375 or 750 nm, respectively. Observation of the 2C2P signal required temporal and spatial overlap of the 375 and 750 nm pulses. The amplitude of the signal depended on the polarization of each beam. 2C2P excitation can have applications in fluorescence microscopy and elsewhere when spatially localized excitation is desirable.     

An alternate synthesis of 6-substituted-5-deazapteridines

A procedure for synthesis of 2,4-diamino-6-substituted-5-deazapteridines (pyrido[2,3-d]pyrimidines) is described. Condensation of 1-piperidino-1-propene with ethoxymethylenemalononitrile afforded an enamino malononitrile adduct, which when treated with ammonia yielded 2-amino-3-cyano-5-methylpyridine. Cyclization to 2,4-diamino-6-methyl-5-deazapteridine could be effected with guanidine. Similar condensation of piperidinopropene with ethyl methoxymethylenecyanoacetate followed by cyclization with hydroxylamine gave 2-amino-3-carbethoxy-6-methylpyridine 1-oxide. Reduction with phosphorus trichloride afforded the pyridine base, however, attempts to cyclize the amino ester to 2-amino-4-hydroxy-6-methyl-5-deazapteridine were unusccessful.     

Nature et stabilité des complexes métalliques de cryptands dinucléants en solution II. Polythiamacrotricycles et monocycles apparentés

Nature and Stability of Some Metallic Complexes of Dinucleating Cryptands in Solution II. Polythiamacrotricycles and Related Monocyclic Subunits The stability constants of the Cu²⁺ and Ag⁺ complexes of the cylindrical macrotricycle 1a (1,7,13,19-tetraaza 4,16-dioxa 10,22,27,32-tetrathiatricyclo[17.5.5.5]tetratriacontane) have been determined by pH-metry, as well as those of the Cu²⁺, Co²⁺, Zn²⁺, Cd²⁺, Pb²⁺, and Ag⁺ complexes of the monocyclic subunit 2a (1,7-dimethyl-1,7-diaza 4,10-dithiacyclododecane), in aqueous solutions (NaClO₄) at 25°. In the Cu(II) systems, equilibria were reached slowly, and the results established by pH-metry were confirmed by UV/VIS spectrophotometric studies. The tricycle 1a forms dinuclear cryptates with copper and silver, with overall stability constants log β₂₁₀ (Cu₂- 1a )⁴⁺ = 18.5, log β_21-2 (Cu₂- 1a (OH)₂)²⁺ = 4.8, log β₂₁₀(Ag₂- 1a )²⁺ = 23.0. Ag⁺ also forms a mononuclear (Ag- 1a )⁺ complex, with log β₁₁₀ = 13.1, but no mononuclear species were detected in the Cu- 1a system. The absorption spectra of the bis-Cu(II) complexes of 1a and 2a in aqueous medium, MeOH and propylene carbonate (PC) are given, as well as those, in MeOH and PC, of the bis-copper complexes of the related monocycles 3 and 4 (1,7-diaza-4,10,13-trithiacyclopentadecane and 1.10-diaza 4,7,13,16-tetrathiacyclooctadecane, respectively), and tricycle 5 with two benzyl groups in the lateral chains. The complexing properties of the polyoxa- and polythia macrotricycles (Parts I and II of this series) are compared to those of other bis-chelating ligands, the bicyclic bis-tren and the monocyclic bis-dien.     

Anionic-initiated polymerization of β-nitrostyrenes

β-Nitrostyrene and many of its derivatives have been shown to yield high polymers via anionic initiation with alkoxide ions in protic solvents, e.g., alcohols. A study was conducted to determine the effect of certain substituents on the polymerization characteristics of representative monomers of this series and the properties of their polymers. A kinetic study was conducted and the relative rates of propagation were unexpectedly found to correlate well with brown's σ⁺ values. The rates of initiation of two representative monomers, β-nitrostyrene and p-methoxy-β-nitrostyrene, with sodium ethoxide were found to be 3.51 and 2.86 liter/mole sec, respectively. The rate of chain transfer in ethanol was studied qualitatively by using gel-permeation chromatography (GPC) to obtain molecular weight distribution (MWD) curves. The low values of the M _w/M _n ratios indicated little chain transfer in the protic solvent.     

Defect formation on surfaces bombarded by energetic multiply charged proteins: Implications for the conformation of gas-phase electrosprayed ions

Indirect information on the conformation of highly charged molecular ions may be obtained by monitoring their collisional cross sections and the course of simple gas-phase reactions such as hydrogen-deuterium exchange. In this work, another indirect but more visually oriented approach is explored: electrosprayed protein ions are accelerated toward a highly oriented pyrolytic graphite surface and the resulting single-ion defects are imaged by scanning force and tunneling microscopy. All protein impacts generated shallow hillocks: the shapes depended on the identity and charge state of the incident protein. Lysozyme and myoglobin, both compact, globular proteins in the native state, produced compact, almost circular hillocks. However, hillocks generated by myoglobin that had been denatured in the solution phase were elongated, and the elongation was positively correlated with the charge state of the ion. It appears that structural information about gas-phase multiply charged proteins can be derived from imprints generated by energetic protein impacts on surfaces.     

Reactive E=C(p‐p)π‐Systems. 56 [1] Attempted Preparation of PhE=C(CF3)2 by Reactions of Hexafluoroacetone with PhE(SiMe3)2 (E = As,P)

The chance to prepare sterically and inductively stabilized arsa‐ and phosphaalkenes of the type PhE=C(CF₃)₂ (E = As, P) by reacting phenyl‐bis(trimethylsilyl)‐arsane ( 1 ) and ‐phosphane ( 5 ), respectively, with hexafluoroacetone (HFA) was investigated. The insertion of the carbonyl function in one of the Si–E bonds was found to occur at temperatures between ?78 and 20 °C. The elimination of hexamethyldisiloxane, which in case of acylamides and ketones spontaneously follows the insertion and in case of RE(SiMe₃)–CR′₂(OSiMe₃) at least can be initiated by solid sodium hydroxide as catalyst, turned out to be impossible for the primary products PhE(SiMe₃)–C(CF₃)₂‐OSiMe₃ [E = As ( 2 ), P ( 6 )]. 2 and 6 were characterized by analytical (C, H) and spectroscopic methods (IR, NMR, MS).     

Coordination chemistry of bidentate diflourophospines IV. Complexes of 1,2-bis(diflourophosphino)ethane with Ni(O) and Mo(O).

The ligand, 1,2-bis(difluorophosphino)ethane, (PF₂C₂H₄PF₂), reacts with Ni(CO)₄ in the gas phase and in solution to produce carbon monoxide and a polymer, [Ni(PF₂C₂H₄PF₂)₂]_x. PF₂C₂H₄PF₂ displaces norbornadiene from (C₇H₈)Mo(CO)₄ to yield the relatively air-stable complex, Mo(CO)₄-(PF₂C₂H₄PF₂). Analysis of the infrared spectrum of the monomeric complex indicates that the ligand exhibits π-acceptor strength equal to PF₂C₆H₁₀PF₂.