New Carbonyl Compounds in the High-Boiling Fraction of Lavender Oil. 3rd Communication

The occurrence of a series of new constituents which can be considered as Diels-Alder adducts of methyl vinyl ketone and ocimene (→1–4), myrcene (→ 9 , 10 ) or β-far-nesene ( → 11 , 12 ), respectively, was reported. Furthermore, the structures of four isomeric cyclohexene derivatives could be established as adducts 21–24 of (E, Z)- and (E, E)-1,3,5-undecatrience and methyl vinyl ketone. Another series of constituents having the norbornane skeleton represents adducts 25–32 , and 33–40 of methyl cyclopentadiene and 1-octen-3-one or methyl vinyl ketone, respectively. In accordance with Alder's endo-rule the endo-isomers are preponderant in the natural as well as in the synthetic mixtures. Most of these constituents could also be identified in a lavender absolute as well as in a freshly prepared hexane extract of lavender flowers (Lavandula officinalis CHAIX ).     

Polysulfonylamine. XLI. Ein Silber(I)-Hydrat ungewöhnlicher Zusammensetzung: Röntgenstrukturanalytische und thermochemische Charakterisierung von Tetrakis(dimesylamido)aquatetrasilber(I) [Ag4(N(SO2CH3)2}4(H2O)]

Polysulfonyl Amines. XLI. A Silver(I) Hydrate with an Unusual Composition: Characterization of Tetrakis(dimesylamido)aquatetrasilver(I) [Ag₄(N)SO₂CH₃)₂}₄(H₂O)] by X-Ray Diffraction and Thermal Analysis The title compound is obtained by crystallizing AgN(SO₂CH₃)₂ from water at room temperature. Crystallographic data (at ?95°C): Triclinic space group P1 , a = 864.6(4), b = 1 211.2(5), c = 1 399.1(5) pm, α = 90.97(3), β = 90.90(3), γ = 98.25(4)°, V = 1.4496 nm³, Z = 2, D_x = 2.608 Mg m^?3. The four independent silver atoms and the water molecule form zigzag chains Ag(1)-Ag(2)-(μ-H₂O)-Ag(3) …? Ag(4) …? Ag(1′) with distances Ag(1)-Ag(2) 309.7, Ag(2)-O(w) 241.8, O(w)-Ag(3) 241.4, Ag(3) …? Ag(4) 342.9, Ag(4) …? Ag(1′) 361.4 pm. The catenated silver atoms are further connected by the dimesylamide anions acting as tridentate bridging (α-O, N, ω-O)-ligands. The resulting strands are interconnected into layers through one O(S)-Ag′ contact (247 pm) and one hydrogen bond O(w)-H(l) …? O′(S) per repeating unit. Between the layers, a weak O(S) …? Ag″ interaction (271 ptn) and a hydrogen bond O(w)-H(2) …? O(S) per repeating unit are observed. The silver atoms Ag(l) to Ag(4) display the coordination numbers 5 [NO,Ag(2), distorted trigonal bipyramid], 5[NO₂,O(w)Ag(I), distorted trigonal bipyramid], 5[O₄,O(w), trigonal bipyramid], and 2 + 1 (N₂, li-near; plus a secondary Ag …? 0 contact). The dehydration of the title compound and a solid-solid phase transformation in anhydrous AgN(SO₂CH₃)₂, were quantitatively investigated by thermoconductometry and time- and temperature-resolved X-ray diffractometry (TXRD).     

Mass spectrometric fragmentation of isomeric 2-alkyl-substituted 1,3-indandiones and 3-alkylidenephthalides: a seven-step consecutive isomerization of regular and distonic molecular radical cations

The electron impact-induced fragmentation of 2,2-dimethyl- and 2-ethyl-1,3-indandione, 1 and 2, and their isomers, 3-isopropylidene- and 3-propylidenephthalide, 3 and 4, respectively, was studied in detail by mass-analysed ion kinetic energy (MIKE) and collision-induced dissociation (CID-MIKE) spectrometry, including ²H and ¹³C. labelled analogues of 1 and 2. In all regimes of internal energy, the molecular ions 1^+. ? 4^+. interconvert by up to seven consecutive, reversible isomerization steps prior to the main fragmentation processes, viz. loss of CH₃^. and C₂H₄. 1,3-Indandione and 3-methylenephthalide ions with identical alkylidene moieties (i.e. 1^+.?3^+. and 2^+.?4^+.) equilibrate rapidly and completely prior to fragmentation, whereas these pairs of isomers interconvert only slowly via a five-step rearrangement of the indandione ions 1^+.?2^+.. Distinct from the behaviour of simpler ionized carbonyl species, a 1,2-C shift of a (formally) neutral carbonyl group is found to occur along with that of a protonated one. Also distinct from simpler cases, methyl loss does not take place from the ionized enol intermediates formed within the interconversion 1^+.?2^+. of the diketone ions but rather from the n-propylidenephthalide ions 4^+.. This follows from CID-MIKE spectrometry of the [M ? CH₃]⁺ ions of 1–4 and two reference C₁₀H₇O₂⁺ (m/z 159) ions of authentic structures (protonated 2-methylene-1,3-indandione and protonated 1,4-naphthoquinone). The characteristic CID fragmentation of the C₁₀H₇O₂⁺ ions is rationalized. Finally, the multistep isomerization of ionized 1,3-indandiones apparently also extends to higher homologues [e.g. 5^+. from 2-ethyl-2-methyl-1,3-indandione (5) and 6^+. from 2,2-diethyl-1,3-indandione (6)]: the ionized phthaloyl group of 1,3-indandione radical cations 1^+., 2^+., 5^+. and 6^+., originally attached with its two acyl functionalities to the same carbon of the aliphatic chain, performs, in fact, a ‘multi-step migration’.     

New Carbonyl Compounds in the High-Boiling Fraction of Lavender Oil. 2nd Communication

In addition to the sesquiterpenoid compounds reported in [1] the in-depth analysis of lavender oil also led to the identification of new constituents with caryophyllane ( 1 – 6 ), cedrane ( 7 and 8 ) and other skeletons ( 9 – 21 ). Spectroscopic properties as well as partial syntheses of these compounds are discussed.     

Intercalation materials for lithium rechargeable batteries

An overview is given of intercalation materials for both the negative and the positive electrodes of lithium batteries, including the results of our own research. As well as lithium metal as a negative electrode, we consider insertion materials based on aluminium alloys. In the case of the positive electrode metal-oxides based on manganese, nickel and cobalt are discussed. Received: 27 May 1997 / Accepted: 30 July 1997     

Influence of the mesophase structure on the β-relaxation in liquid crystalline poly(meth)acrylates

The dependence of the rotation of the mesogenic unit around its long axis (β-relaxation) on the actual mesophase in liqid crystalline polymethacrylates and polyacrylates was studied by dielectric spectroscopy in the frequency range from 10⁻² Hz to 10⁶ Hz and in a temperature range from 170 K to 430 K. As mesogenic units derivatives of (p-alkoxy-phenyl)-benzoate were used where different mesophases were achieved by small variation of the mesogenic structure, the spacer length and the tail group of the mesogenic unit. For all samples the temperature dependence of the relaxation rate of the β-relaxation can be described by an Arrhenius equation where both the pre-exponential factor and the activation energy increase significantly with the order of the mesophase. To characterize the structure X-ray measurements were also carried out. The mean lateral mesogenic distance was correlated directly with relaxational quantities.