The reactivity of mono-substituted HC=CR (R =Ph. a; CH2OH, b; CH2CH2CH2CH3, c) and di-substituted RC=CR (R = CH2CH3, d; CO2CH3, e; Ph. f) acetylenes was studied in supercritical carbon dioxide (scCO(2)) using the easily available complex CpCo(CO)(2) as catalyst. The reaction of phenylacetylene produced a mixture of the isomeric cyclotrimers 1,3,5- (2a) and 1.2,4-triphenylbenzene (2a '). in a 1:5 ratio, and traces of cobaltcyclopentadienone complexes CPCO(eta (4)-C4H2[Ph](2)CO) (6a, mixture of isomers). The possible product formed by the incorporation of CO, to alkynes, i.e. diphenylpyrone (7a) was not observed. The reaction of the cobaltacyclopentadiene complex CpCo(1.4-sigma -C-4[Ph](4))(PPh)(3) (8f), in scCO(2), was performed. No insertion of CO2 into the Co-C a-bond to form tetraphenylpyrone (7f) by reductive elimination was observed, instead the cobaItcyclobutadiene Complex CpCo(eta (4)-C-4[Ph](4)) (9f) was formed. In the reactions with other alkynes, lower yields were obtained in general, except in the cyclotrimerisation of the highly activated alkyne, propargyl alcohol (b). Reaction of the non-activated alkynes, 1-hexyne (c) and 3-hexyne (d), produced complex mixtures of cobalt complexes in low yield in which the alkyne was coordinated to cobalt. Finally, the highly hindered diphenylacetylene (f) gave a mixture of the known Complexes CpCo(eta (4)-C-4[Ph](4)) (9f) and CpCo(eta (4)- C-4[Ph](4)CO) (6f) in agreement with the results observed in conventional organic solvents. (C) 2001 Elsevier Science B.V, All rights reserved.

The reactivity of arylisocyanates in supercritical carbon dioxide (scCO(2)) was studied using the easily available complexes CpCo(CO)(2), CpCoPPh3Me2 and Ni(cod)(2) as catalysts. A study of the solubility of the catalysts in scCO(2) was undertaken in all cases. The complex CpCo(CO)(2) is very soluble, 1.7 x 10(-1) mol kg(-1), while CpCoPPh3Me2 has a lower solubility, 7.2 x 10(-3) mol kg(-1), and Ni(cod)(2) is insoluble in scCO(2). For comparison purposes, the reactions were performed in parallel in scCO(2), using toluene as a solvent and just with the neat liquid arylisocyanate. Reactions in scCO(2) either do not take place at all, when CpCo(CO), is used as catalyst, or occur with low yields affording the trimer of the corresponding arylisocyanate when CpCoPPh3Me2 or Ni(cod)(2) act as catalysts. No incorporation of CO2 into the organic substrate was observed. Better conversions to triarylisocyanate were obtained when the reactions were performed by direct mixture of the liquid arylisocyanate ArNCO (Ar = Ph, p-CH3C6H4, p-CH3OC6H4) and the catalyst. Using toluene as a solvent, the yields of the trimers were lower than those obtained in neat arylisocyanate, and in some cases they were not formed at all. For instance in the reaction of CpCo(CO), and tolylisocyanate either under stoichiometric or catalytic conditions the trimer is not obtained, instead the compound H2R3N3C2O2 (R = CH3C6H4), was isolated in low yield. In the reaction of Ni(cod)(2)/PPh3 with phenylisocyanate, the trimer was formed but in low yield. The lower yields of the trimers observed when the reactions were performed in scCO(2) or in toluene, compared to that observed in neat arylisocyanates, indicates that the decrease in reactivity is due to a decrease in concentration. (C) 2001 Elsevier Science B.V. All rights reserved.

n/a

n/a

A new ornithopod dinosaur is described here under the name of Draconyx loureiroi n. gen., n. sp. on teeth, caudal vertebrae, forelimb, hindlimb, and foot material that were found in association in the Late Jurassic-Tithonian of Lourinhã, Portugal. Draconyx is a Camptosauridae related to Camptosaurus.

n/a

In this paper we deal with the interpolation from Lebesgue spaces \(L^p\) and \(L^q\), into an Orlicz space \(L^\varphi\), where \( 1 \le p < q \le \infty \) and \(\varphi^{-1}(t)=t^{1/p}\rho(t^{1/q-1/p})\) for some concave function \(\rho\), with the special attention to the interpolation constant \(C\). For a bounded linear operator \(T\) in \(L^p\) and \(L^q\), we prove modular inequalities, which allow us to get the estimate, for both, the Orlicz norm and the Luxemburg norm,
\[
\|T\|_{L^\varphi\to L^\varphi}
\le C\max\Big\{
\|T\|_{L^p\to L^p},
\|T\|_{L^q\to L^q}
\Big\},
\]
where the interpolation constant \(C\) depends only on \(p\) and \(q\). We give estimates for \(C\), which imply \(C<4\). Moreover, if either \( 1 < p < q \le 2\) or \( 2 \le p < q < \infty\), then \(C< 2\). If \(q=\infty\), then \(C\le 2^{1-1/p}\), and, in particular, for the case \(p=1\) this gives the classical Orlicz interpolation theorem with the constant \(C=1\).