Synthesis of N-alkyl derivatives of 4-(2′-aminoethyl)indole

N-Substituted 4-(2′-aminoethyl)indoles are attainable in good yields from indole-4-acetic acid ( 2 ). Several methods of preparation for 2 were tried or considered. A new sequence involving Arndt-Eistert homologation of indole-4-carboxylic acid has been devised, which is no more laborious than a literature homologation sequence involving indole-4-acetonitrile, and which provides somewhat better overall yields than the literature method.     

A minimization problem related to the estimation of a lower bound for the temperature in a free boundary value problem related to the combustion of a solid

This paper investigates the least time τ_* of the first zero of the bounded solution to an initial boundary value problem for the heat equation. The heat equation is considered in the domain $$\left\{ {(x,t)| - \infty< x< s(t),0< t \leqslant T} \right\}$$ . The initial conditionu(x, 0)=φ(x) and the boundary conditionu _x (s(t),t)=?R are specified. Let τ=τ(φ,R, s) denote the first zero ofu onx=s(t), that is,u(s(τ), τ)=0. Let τ_*=min τ, where the minimum is taken over a class of functionss=s(t). The existence of τ_* is demonstrated, and a generalization of the problem is discussed.     

Borylation of aryldiazonium ions with N-heterocyclic carbene-palladium catalysts formed without added base

[reaction: see text] A highly efficient catalytic borylation process with aryldiazonium ions was developed using a carbene-palladium catalyst formed in situ to give arylpinacolatoborane products. An X-ray structure for the N-heterocyclic carbene-palladium complex, used as the catalyst formed from bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolium chloride, was obtained without added base.     

Recognizing constant curvature discrete groups in dimension 3

We characterize those discrete groups which can act properly discontinuously, isometrically, and cocompactly on hyperbolic -space in terms of the combinatorics of the action of on its space at infinity. The major ingredients in the proof are the properties of groups that are negatively curved (in the large) (that is, Gromov hyperbolic), the combinatorial Riemann mapping theorem, and the Sullivan-Tukia theorem on groups which act uniformly quasiconformally on the -sphere.

     

The Low Temperature Processing of Titanium Dioxide Films by the Addition of Trimesic Acid

Sol-gel deposited titanium dioxide films are used for a wide range of applications. One of the drawbacks to these films is that they must be heated in excess of 400^∘C in order to obtain durability. We have found that the processing temperature required to prepare sol-gel derived titanium dioxide films can be significantly reduced by the addition of small amounts of trimesic acid. The addition of this material provides a low energy pathway for the growth of titanium dioxide particles. Titanium dioxide films prepared with trimesic acid show significantly enhanced physical properties with respect to cracking and peeling. Scanning Electron Microscopy and X-Ray Diffraction analyses of films are presented.     

Electronic interaction in an outer-sphere mixed-valence double salt: a polarized neutron diffraction study of K(3)(MnO(4))(2)

The mixed-valence double salt K(3)(MnO(4))(2) crystallizes in space group P2(1)/m with Z = 2. The manganese centers Mn1 and Mn2 constitute discrete "permanganate", [Mn(VII)O(4)](-), and "manganate", [Mn(VI)O(4)](2-), ions, respectively. There is a spin-ordering transition to an antiferromagnetic state at ca. T = 5 K. The spin-density distribution in the paramagnetic phase at T = 10 K has been determined by polarized neutron diffraction, confirming that unpaired spin is largely confined to the nominal manganate ion Mn2. Through use of both Fourier refinement and maximum entropy methods, the spin on Mn1 is estimated as 1.75 +/- 1% of one unpaired electron with an upper limit of 2.5%.     

Asymmetric glycolate aldol reactions using cinchonium phase-transfer catalysts

Cinchona phase-transfer catalysts (PTC) were developed for glycolate aldol reactions to give differentially protected 1,2-diol products. Silyl enol ether 9 reacted to generate benzhydryl-protected products. O-Allyl trifluorobenzyl cinchonium hydrofluoride CN-4 (20 mol %) catalyzed the addition of 9 to benzaldehyde to give 8 as a single syn-product in 76% yield and 80% ee. Recrystallization enriched the product to 95% ee, and a Baeyer-Villiger reaction transformed the product into useful ester intermediates. [reaction: see text]     

Synthesis of novel 2-azabicyclo[2.2.0]- and [2.1.1]hexanols

Methyl- and phenyl-substituted N-(ethoxycarbonyl)-2-azabicyclo[2.2.0]hex-5-enes 6 were reacted with NBS in wet DMSO to afford bromohydrins. Mixtures of unrearranged 6-exo-bromo-5-endo-hydroxy-2-azabicyclo[2.2.0]hexanes 7a,b and rearranged 5-anti-bromo-6-anti-hydroxy-2-azabicyclo[2.1.1]hexanes 8a,b were formed stereoselectively from the parent alkene 6a and 4-methyl alkene 6b. The 5-methyl alkene 6c affords only unrearranged bromohydrin 7c and dibromohydrin 9. By contrast, solely rearranged 3-endo-substituted-2-azabicyclo[2.1.1]hexane bromohydrins 8d-f result from additions to 3-endo-methyl alkene 6d, 3-endo-4-dimethyl alkene 6e, and 3-endo-phenyl alkene 6f. As an alternative route to bromohydrins, the parent 5,6-exo-epoxide 10a and 5-endo-methyl-5,6-exo-epoxide 10b were ring opened with bromine/triphenylphosphine to afford unrearranged 5-endo-bromo-6-exo-hydroxy-2-azabicyclo[2.2.0]hexanes 11a,b, while the 3-endo-methyl epoxide 10c afforded solely the rearranged 5-anti-bromo-6-anti-hydroxy-3-exo-methyl-2-azabicyclo[2.1.1]hexane isomer 8g. Tributyltin hydride reduction of bromohydrins 7a,b and 11a afforded novel 2-azabicyclo[2.2.0]hexan-5-ols 13a,b and -6-ol 14, and bromohydrins 8a,b, 8d-g afforded new 2-azabicyclo[2.1.1]-hexan-5-ols 15a,b and 15d-g.     

Hydro­gen bonding in substituted nitro­anilines: isolated nets in 1,3‐­diamino‐4‐nitrobenzene and continuously interwoven nets in 3,5‐­dinitro­aniline

Molecules of 1,3‐diamino‐4‐nitrobenzene, C₆H₇N₃O₂, are linked by N—H?O hydrogen bonds [N?O 2.964 (2) and 3.021 (2) Å; N—H?O 155 and 149°] into (4,4) nets. In 3,5‐di­nitro­aniline, C₆H₅N₃O₄, where Z′ = 2, the mol­ecules are linked by three N—H?O hydrogen bonds [N?O 3.344 (2)–3.433 (2) Å and N—H?O 150–167°] into deeply puckered nets, each of which is interwoven with its two immediate neighbours.