351 nm, 0.7 ns laser damage thresholds of monomeric liquid-crystalline systems

The 351 nm laser-damage thresholds (at 0.7 nm pulse length) of monomeric liquid crystals are reported and results from aromatic-core samples are compared with those from fully saturated systems. The role of π-electron conjugation is examined and identified as the key cause for laser damage. For UV laser compatibility of devices, the damage behaviour of an alignment-layer polymer (nylon 6/6) was also investigated.     

Off-shell behaviour of theN-N interaction in a six-quark resonating group model of the deuteron

Two different 6-quark resonating group models of the deuteron are investigated to study the off-shell property of theN-N interaction. In the first model the quarks interact by a central one-gluon-exchange potential plus confinement potential. The meson-exchange contribution to then-p potential is simulated by a central GaussianN-N potential. In the second model the quarks interact by one-gluon-and one-pion-exchange potentials (central and noncentral) plus confinement potential. A small additional -exchange potential between neutron and proton binds the deuteron at the correct energy.Several off-shell variants of the two resonating group models are compared with each other by analyzing their elastic electron scattering cross sections. It is found that the standard renormalized version of the resonating group model yields potentials and wave functions that may be considered physical within the limitations of the model. Unitary off-shell transformations, which modify potentials and wave functions in any sizeable way, lead to a disagreement between the charge distribution predicted by the model via analysis of electron scattering and the charge distribution following from the microscopic quark distribution.Both of the 6-quark models support a soft repulsive core of the tripletn-p potential with a core height of around 900 MeV.     

Kinetik und stereochemischer Verlauf der thermischen Umlagerung der vier stereoisomeren Propenyl-(but-2′-enyl)-äther

The gas-phase rearrangement of (1Z, 2′E)-, (1Z, 2′Z)-, (1E, 2′E)-, and (1E, 2′Z)- propenyl but-2′-enyl ether (Z, E)-, (Z, Z)-, (E, E)-, and (E, Z)-1) into erythro- and threo-2, 3-dimethyl-pent-4-en-al (erythro- and threo-2) was investigated over a temperature range from 142,5° to 190,0° at 20–35 Torr (for kinetic data and activation parameters see table 2). All four stereoisomeric ethers 1 rearrange preferentially via a chair-like transition state C into the aldehydes 2 (ΔΔG^≠ (160°) = 2,5–2,7 kcal/mol for B – C (B = boat-like transition state). The relative rates (k_rel) for (Z, Z)-1, (Z, E)-1, (E,Z)-1, and (E,E)-1 at 160° are 1,0, 2,9, 4,3 and 9,0 respectively (see table 5). Taking into account the relative enthalpies of the ethers 1 and the steric interaction in the C transition state of the ethers 1 (see table 6), k_rel values can be estimated. They are in good agreement with those observed (see table 5).     

Thermisches Verhalten von Cyclopropa[c]chromenen

The Cyclopropa[c]chromenes 14 , trans-and cis- 15 , trans-and cis- 16 and 17 rearrange on heating > 200° in N, N-diethylaniline to give 2-alkyl-2H-chromenes 7, 8, 21, 22. The rate determining step of this rearrangement is the ‘homoelectrocyclic’ ring opening of the cyclopro-pa[c]chromenes to give ω-allyl-quinomethanes of type 4. These intermediates show fast [1,5s] and [1,7a] H-shifts, followed by electrocyclic ring closure. Deuterium labelling experiments are in agreement with this mechanism. The remarkable dependence of the rates of rearrangement with respect to the stereochemistry of the cyclopropa[c]chromenes (cf. table 2) suggests that in the first step only one of the two possible disrotatory modes of ring opening is involved.     

Alstonia scholaris: Struktur des Indolalkaloides Narelin

Alstonia scholaris: The structure of the indole alkaloid nareline Besides the known akuammidine, picralinal, picrinine and pseudoakuammigine a new indole alkaloid called nareline (M=352) was isolated from Alstonia scholaris R. BR. , which belongs to the plant family of Apocynaceae. Its structure 2 was deduced by single crystal X-ray diffraction. 2 represents the absolute configuration. The spectroscopic data of 2 and its derivatives (Scheme 1) as well as their chemical behavior support this structure. In biogenetic sense nareline is related to the bases akuammiline ( 4 ) and picraline ( 5 ) (Scheme 2). In contrast to those the C-atom 5 is exocyclic and represents an aldehyde group which forms together with the oxygen atom of the N (4)-hydroxylamine group a cyclic half acetale. - By oxidation (CrO₃/CH₃COOH) of 2 the oxindol derivative 19 (oxonareline) is formed which contains a cyclic acetal as a partial structure element (Scheme 4).     

Kinetik und Mechanismus der Diazotierung, 18. Mitt.: Kinetik und Mechanismus der Diazotierung des Anilins in chlorwasserstoffsaurem Methanol

Ohne ZusammenfassungI.H. Schmid undG. Muhr, Ber. dtsch. chem. Ges.70, 421 (1937); II.H. Schmid, Z. Elektrochem.43, 626 (1937); III.H. Schmid, Atti X. Congr. internat. Chim. Roma2, 484 (1938); IV.H. Schmid undA. Woppmann, Mh. Chem.83, 346 (1952); V. und VI.H. Schmid undR. Pfeifer, Mh. Chem.84, 829, 842 (1953); VII.H. Schmid, Mh. Chem.85, 424 (1954); zusammenfassender Ber.:H. Schmid, Chemiker-Ztg.78, 565, 683 (1954); VIII.H. Schmid, Mh. Chem.86, 668 (1955); IX.H. Schmid undA. F. Sami, Mh. Chem.86, 904 (1955); X.H. Schmid undE. Hallaba, Mh. Chem.87, 560 (1956); XI.H. Schmid undA. Woppmann, Mh. Chem.88, 411 (1957);H. Schmid, Mh. Chem.88, 161, 344 (1957); XII.H. Schmid undM. G. Fouad, Mh. Chem.88, 631 (1957);H. Schmid, Österr. Pat. 191 399, Kl. 12e₂ (Juni 1957);H. Schmid, Chemiker-Ztg.81, 603 (1957); XIII. und XIV.H. Schmid undCh. Essler, Mh. Chem.88, 1110 (1957);90, 222 (1959); XV.H. Schmid undA. Woppmann, Mh. Chem.90, 903 (1959); XVI.H. Schmid undCh. Essler, Mh. Chem.91, 484 (1960); XVII.H. Schmid undG. Muhr, Mh. Chem.91, 1198 (1960);H. Schmid, Mh. Chem.92, 174 (1961).     

Zur Photochemie von Allylaryläthern. 55. Mitteilung über Photoreaktionen

The photochemical reactions of different allyl aryl ethers (Scheme 3) were investigated in hydrocarbons (Chap. 3.1) and in alcoholic solvents (Chap. 3.2). The composition of the photoproducts depended very much on the nature of the solvent. Irradiation (3–95 h) of different methyl substituted allyl aryl ethers ( 1, 3, 5, 7 and 11 ) with a low pressure mercury lamp (λ_Emiss. = 254 nm; 6 or 15 Watt) under argon (quartz vessel) resulted in the formation of 2-, 3– and 4-substituted phenols, dienones and products of consecutive reactions (Tables 1–4 and 6). The results suggested that all products were formed by homolytic cleavage of the C? O bond in the singlet state of the ethers to intermediate radical-geminates (Scheme 5) followed by radical recombination of the two fragments. No products were formed by concerted processes (Table 5, Schemes 5 and 6). Upon irradiation of allyl aryl ethers lacking alkyl substituents at position 4 ( 1 and 5 ) in protic solvents, mainly 2- and 4-allylated phenols were obtained (Tables 1 and 4); 3-allylated phenols were formed only in small amounts (0.02%). However, in aromatic hydrocarbons or cyclohexane 3-allylated phenols were obtained from 1 , 5 and 11 in significant amounts (3–11%; Tables 1, 4 and 6). E.g., upon irradiation of allyl-2,6-dimethyl-2,4-cyclohexadien-1-one ( 6 ) besides 3- and 4-allyl-2, 6-dimethyl-phenol ( 23 and 24 ). Irradiation of 5 in methanol afforded 23 and 6 only in traces, whereas 24 was the main product.