The madelung synthesis of dihydro-1H-pyrrolo- and tetrahydropyrido[1,2-a]- indoles under mild conditions

Benzeneacetonitriles substituted with lactam moieties in the ortho-position cyclize under the influence of a base, dependent on the ring-size of the lactam function, to dihydropyrrolo-, tetrahydropyrido[1,2-a]indole or dihydro-1-benzazepin derivatives, respectively

On the mechanism of the reaction of enamines and dimethyl acetylenedicarboxylate (DMAD) in polar and apolar solvents

[2+2]-Cycloadducts of enamines and DMAD, formed in apolar solvents, isomerize to pyrrolizine derivatives under mild conditions in protic polar solvents like methanol and 1-butanol

Synthesis of pyrrolizines by intramolecular capture of 1,4-dipolar intermediates in reactions of enamines with dimethyl acetylenedicarboxylate

Solvent polarity and reaction temperature strongly influence the reactions of dimethyl acetylenedicar-boxylate (DMAD) with 1-pyrrolidinyl enamines of acyclic and cyclic ketones. Whereas DMAD and 1-[1-phenyl-2-(phenylthio)ethenyl]pyrrolidine (3) give only a mixture of the isomeric 1,3-butadienes (5) in apolar solvents, in methanol the main product is the pyrrolizine 7, together with 5. Again in methanol, DMAD reacts at 0-5° with 8, 9 and 10 to give exclusively 1:1 adducts, the pyrrolizines 11,12 and 13, respectively, whereas at −50° 8 and 9 give 1:2 (enamine : DMAD) adducts, the pyrrolizines 14 and 15, respectively; a single crystal X-ray analysis of 14 gave the structure of the 1:2 adducts. In the same solvent methyl propiolate and 8 give only the linear Michael adduct 17. The enamine-ketone 18 reacts with DMAD in propylene carbonate at 0–5° to give, via (2 + 2)-cycloaddition and ring expansion, 19, and the linear Michael adduct 20. The mechanism of (2 + 2)-cycloaddition and pyrrolizine formation is discussed in terms of a common tied-ion pair intermediate formed in the first, rate-determining step, followed by a second solvent-dependent step

Fabrication of pure gold nanostructures by electron beam induced deposition with Au(C0)CI precusor: deposition characteristics and primary beam scattering effects

In the search for a direct write, high-purity electron beam induced deposition (EBID) process, a new gold precursor that is commonly available is investigated. This precursor, Au(CO)Cl, can indeed be used to produce a high-purity golden nanostructure (>95 at% Au), at a wide variety of electron beam parameters. The use of a mass spectrometer to determine the components of the actual precursor vapour showed that the Au(CO)Cl density in the vapour is very low (estimated a

Cognitive animacy and its relation to linguistic animacy: Evidence from Japanese and Persian

Animacy, commonly defined as the distinction between living and non-living entities, is a useful notion in cognitive science and linguistics employed to describe and predict variation in psychological and linguistic behaviour. In the (psycho)linguistics literature we find linguistic animacy dichotomies which are (implicitly) assumed to correspond to biological dichotomies. We argue this is problematic, as it leaves us without a cognitively grounded, universal description for non-prototypical cases. We show that ‘animacy’ in language can be better understood as universally emerging from a gradual, cognitive property by collecting animacy ratings for a great range of nouns from Japanese and Persian. We used these cognitive ratings in turn to predict linguistic variation in these languages traditionally explained through dichotomous distinctions. We show that whilst (speakers of) languages may subtly differ in their conceptualisation of animacy, universality may be found in the process of mapping conceptual animacy to linguistic variation

Reduction of nitro groups by ynamines; synthesis and x-ray crystal structure of n,n-diethyl-3,3a-dihydro-3-methylbenzofuro[3,2-c]isoxazole-3-carboxamide

3-Nitrobenzo[b]furan and 1-diethylaminopropyne react thermally at 5–10°C to give a 1:1 addition product ( ) in which one of the oxygen atoms of the nitro group is transferred to C-1 of the acetylene. The structure of the benzofuro[3,2-c]isoxazole ( ) has been determined by X-ray crystallography