Synthesis,proton NMR stereochemical study and diels-alder reaction of (E)-7-arylidene-2H,6H-naphtho[1,8-bc]furan-2,6-diones

7-Arylidene-2H,6H-naphtho[1,8-bc]furan-2,6-diones 3 were prepared by a retro-Diels-Alder reaction of the corresponding dihydro 1,3-oxazines 2 or in a one pot synthesis from 6-hydroxy-2H-naphtho[1,8-bc]furan-2-one 1 . Their E configuration was established from the chemical shift's values of the vinylic proton and by ¹H nmr NOE difference spectroscopy. Cycloadditions of 3b upon styrene or stilbene were catalyzed by boron trifluoride etherate. The cycloadducts were obtained with the relative trans configuration.     

Palladium-catalyzed carbon-carbon bond-forming 1,2-ligand migration of organoalanes

A one-pot, two-step process that transforms terminal alkynes into ethyl methyl-substituted benzylic quaternary carbon centers is described. (E)-2,2-Disubstituted-1-alkenyldimethylalanes have been shown to participate in 1,2-alkyl migration from aluminum to carbon with concomitant arylation at the 2-position to furnish ethyl methyl-substituted benzylic quaternary carbon centers, when reacted intramolecularly with aryl halides and triflates in the presence of a Pd(0) catalyst. The protocol is initiated with Cp2ZrCl2-catalyzed methylalumination of terminal alkynes followed by palladium-catalyzed intramolecular arylation of the resulting (E)-2,2-disubstituted-1-alkenyldimethylalanes, leading to 1,2-methyl shift from aluminum to carbon. In that sequence, a total of three new C-C single bonds are made, and two of the three alkyl groups on Me3Al transferred to the substrate on vicinal carbons. This method was applied to a variety of substrates, and the mechanism was investigated by deuterium-labeling experiments, which revealed that protodealumination of the final dialkylaluminum triflate or halide intermediates by CH3CN results in the formation of the fourth bond in the course of the transformation.     

Immobilizing a Fluorescent Dye Offers Potential to Investigate the Glass/Resin Interface

Silane coupling agents are commonly applied to glass fibers to promote fiber/resin adhesion and enhance durability in composite parts. In this study, a coupling agent multilayer on glass was doped with trace levels of the dimethylaminonitrostilbene (DMANS) fluorophore. The fluorophore was immobilized on the glass surface by tethering the molecule to a triethoxy silane coupling agent, creating the DMANS/silane coupling agent molecule (DMSCA). DMSCA was then diluted with commonly used coupling agents and grafted to a glass microscope coverslip to create a model composite interface. A 53-nm blue shift in fluorescence from the immobilized DMSCA can be followed during cure of an epoxy resin overlayer, giving this technique potential to monitor the properties of the fiber/resin interface during composite processing. Contact angle measurements on these coupling agent layers were similar in the presence or absence of the DMSCA molecule, suggesting that trace levels of the fluorescent probe did not affect the structure of the layer. The immobilized DMSCA molecule behaved similarly to the DMANS precursor in solution. Both showed longer wavelength fluorescence in more polar environments. Copyright 2000 Academic Press.     

Multiresidue method for the determination of residues of 251 pesticides in fruits and vegetables by gas chromatography/mass spectrometry and liquid chromatography with fluorescence detection

A method is described for the determination of 251 pesticide and degradation product residues in fruit and vegetable samples. Extraction of the sample with acetonitrile is followed by a salting-out step. Co-extractives are removed by passing a portion of the acetonitrile extract through an octadecyl (C18) solid-phase extraction cleanup cartridge and then, in a second cleanup, through a carbon cartridge coupled to an amino propyl cartridge. Determination is by gas chromatography with mass-selective detection in the selected-ion monitoring mode, and by liquid chromatography with post-column reaction and fluorescence detection for N-methyl carbamates. The method has been used for analysis of various fruits and vegetables, such as apple, banana, cabbage, carrot, cucumber, lettuce, orange, pear, pepper, and pineapple. Limits of detection range between 0.02 and 1.0 mg/kg for most compounds. Over 80% of the compounds have a limit of detection of < or = 0.04 mg/kg.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Structural and magnetic phase transitions in Pr2NiO4

Neutron powder diffraction and magnetization measurements have been performed in stoichiometric Pr₂NiO₄₊(0), which at room temperature (RT) is orthorhombic (Bmab). Ni²⁺ becomes three dimensionally (3D) antiferromagnetically ordered atT _N 325K, with a propagation vectork=[100], and spins oriented along thea axis (parallel to the propagation vector). The magnetic structure belongs to the _7g (––+)-representation (g _x mode, Shubnikov groupB _pmab') ofBmab, and a magnetic moment of 1.5 _B is measured at 155K. This compound undergoes two different structural phase transitions. First, going down in temperature, Pr₂NiO₄ transforms by a first order phase transition from orthorhombic (Bmab) to tetragonal (P4₂/ncm) atT _c1115K. At high temperature, we can predict a transformation from orthorhombic (Bmab) to tetragonal (I4/mmm) in a continuous way. The extrapolated temperature for this second structural transition isT _c21500±100K. The low temperature structural transformation allows a change in the magnetic structure which forT<T _c1 is better described in the orthorhombic symmetry. Just belowT _c1 the magnetic structure is described by the: _3g (–+)-representation ofPccn(g_xc_yf_z mode, Shubnikov groupPccn), this magnetic phase begins to disappear going down in temperature and at the same time a new magnetic phase grows. This new magnetic structure is described by the _1g ofPccn (c _xg_ya_z mode, Shubnikov groupPccn). Both magnetic structures coexist in a certain temperature range. At 1.5 K thec _xg_ya_z mode represents the total of the magnetic ordering. To reproduce the observed magnetic intensities we are forced to consider that Pr³⁺ is polarized below 40 K, with a magnetic structure which is coupled to the Ni sublattices (i.e. _1g and _3g ). The magnetic moment at low temperature for Pr is about 1.28 _B .