On the regular heptagon

The geometry of rings with 5, 6, 7, 8 and 9 links, particularly those with seven links such as occur in cyclo‐heptane and analogous molecules* is re‐considered with the aid of distance geometry, now more practicable with modern mathematical software. Use is made of a quadric surface which may be fitted to nine points. *In admiration for the author I have ventured to appropriate the title of Archimedes’ work “On the regular heptagon”, which came to light only in 1926 [C. Schoy, Graeco‐Arabische Studien, Isis 8 (1926) 21–40]. “Regular”, as applied to rings in space admits of various definitions. This revised version was published online in July 2006 with corrections to the Cover Date.     

A simple procedure for the chromatographic analysis of nanoliter samples

A simple method for the analysis of nanoliter droplets is proposed, which is profitable when larger samples cannot be collected as, for instance, in the case of several biological fluids and particularly in clinical chemistry. A glass capillary associated to a micromanipulator is used to collect submicroliter volumes which are partially transferred into transparent polymeric tubings with known internal diameters (120–178 μm), where the volumes sampled are measured by meniscus collimations with a collimator microscope at suitable magnification. Both ends of these tubings are preliminarily equipped with ferrules and fittings, so as to make them suitable for connection as the loop to a conventional high-pressure injection valve. The reliability of this procedure has been tested for the analysis of Na⁺, K⁺ and Ca²⁺ present in minute synthetic standard samples (10–200 nL) by a conventional ion-chromatographic instrumentation. Relative standard deviations in peak area measurements (5–6%) are discussed in terms of the whole approximation affecting volume measurements, which depends on both the inconstancy of the inner diameter of the polymeric tubings employed and the uncertainty characterizing meniscus collimations. The proposed procedure can be easily extended to the determination of any organic or inorganic species present in very small samples, provided that their detection can be achieved by any chromatographic approach or, more generally, by flow injection analysis. Received: 16 June 1997 / Revised: 12 August 1997 / Accepted: 14 August 1997     

Studies in polyphenol chemistry and bioactivity. 4.(1) Synthesis of trimeric,tetrameric, pentameric,and higher oligomeric epicatechin-derived procyanidins having all-4beta,8-interflavan connectivity and their inhibition of cancer cell growth through cell cycle arrest

We report an improved synthesis of bis(5,7,3',4'-tetra-O-benzyl)epicatechin 4beta,8-dimer (3) from 5,7,3',4'-tetra-O-benzylepicatechin (1) and 5,7,3',4'-tetra-O-benzyl-4-(2-hydroxyethoxy)epicatechin (2) by replacing the previously employed Lewis acid, titanium tetrachloride, with the clay mineral Bentonite K-10. Under the same conditions, the benzyl-protected all-4beta,8-trimer, -tetramer, and -pentamer were obtained regioselectively from their lower homologues, albeit in rapidly decreasing yields. Reaction of 2 with an organoaluminum thiolate generated from 2-mercaptobenzothiazole and trimethylaluminum followed by acetylation produced 3-O-acetyl-4-[(2-benzothiazolyl)thio]-5,7,3',4'-tetra-O-benzylepicatechin (12). Medium-sized protected oligomers with 4beta,8-interflavan linkages are obtained in improved yields by using this compound as the electrophile and silver tetrafluoroborate as activator and are isolated by reversed-phase HPLC. Their deprotection by ester saponification followed by hydrogenolysis yielded the free procyanidins, which were characterized as their peracetates. The synthetic procyanidins are identical by normal-phase HPLC with fractions isolated from cocoa. The principle of chain extension by two members was demonstrated using a dimeric electrophile obtained by self-condensation of compound 12. Both the synthetic and natural pentamer 32 inhibit the growth of several breast cancer cell lines. Using the MDA MB 231 line, it was established that this outcome is based on the induction of cell cycle arrest in the G0/G1 phase. Subsequent cell death is more likely necrotic rather than apoptotic. Control experiments demonstrate that the polyphenol itself, rather than hydrogen peroxide potentially formed by its autoxidation, is the causative agent.     

Reactions of alkynes with bis(triphenylphosphine)platinum-ethylene: A P-{H} NMR study

Internally consistent assignments of the ³¹P-{¹H} NMR parameters of the complexes [Pt(RCCR′)(PPh₃)₂] are proposed, based on the premise that the magnitude of ¹J(PtP) depends mainly on the nature of the moiety CR trans to P. For a given R, ²J(PP) correlates with ¹J(PtP) for thebond trans to CR. The alkynes PhCCSnEt₃, PhCCSnPh₃, Me₃SiCCCl, Me₃SiCCBr, Et₃SiCCI and MeCCI undergo oxidative addition reactions with [Pt(C₂H₄)(PPh₃)₂]; the intermediate alkyne complex was detected for PhCCSnEt₃, Me₃SiCCCl and Me₃CCBr. The triyne Me(CC)₃Me forms platinum(0) complexes by coordination with the central or terminal CC bond and appears also to give a platinum(II) complex by oxidative addition.     

The Structure of Silylated Amides: N-Methyl-N-Trimethylsilyltrifluoroacetamide,a Reassignment of structure

The ²⁹Si and ¹⁴N nmr spectra of some bissilylamides and monosilylamides are reported. The results are compared with those for model silylesters, amines and imines. The compound of formula CF₃CONCH₃Si(CH₃)₃ (MSTFA) is shown to exist as a tautemeric mixture of a silylamide and a silylimidate. This assignment is confirmed by ¹³C nmr. A rationale is proposed for the structure directing effect of substituents on the amide carbon atom.     

Structural studies of ammonia and metallic lithium-ammonia solutions

The technique of hydrogen/deuterium isotopic substitution has been used to extract detailed information concerning the solvent structure in pure ammonia and metallic lithium-ammonia solutions. In pure ammonia we find evidence for approximately 2.0 hydrogen bonds around each central nitrogen atom, with an average N-H distance of 2.4 A. On addition of alkali metal, we observe directly significant disruption of this hydrogen bonding. At 8 mol % metal there remains only around 0.7 hydrogen bond per nitrogen atom. This value decreases to 0.0 for the saturated solution of 21 mol % metal, as all ammonia molecules have then become incorporated into the tetrahedral first solvation spheres of the lithium cations. In conjunction with a classical three-dimensional computer modeling technique, we are now able to identify a well-defined second cationic solvation shell. In this secondary shell the nitrogen atoms tend to reside above the faces and edges of the primary tetrahedral shell. Furthermore, the computer-generated models reveal that on addition of alkali metal the solvent molecules form voids of approximate radius 2.5-3.0 A. Our data therefore provide new insight into the structure of the polaronic cavities and tunnels, which have been theoretically predicted for lithium-ammonia solutions.     

A molecular orbital study of the changing role ofd-orbitals in transition metal compounds: ZnS,FeS and CrS

SCF-MO studies as FeS, CrS and ZnS illustrate the changing role ofd-orbitals along a transition series, where they become at first good acceptors playing an important role in the bonding, then so stable that their electrons behave essentially as “core” electrons in agreement with the conjecture of Phillips and Williams [1].     

The Isolation,Structure, and Synthesis of Davana Ether,an Odoriferous Compound of the Oil of Artemisia pallens Wall.

Several stereoisomers of 2,6,10-trimethyl-2:5, 7:10-diepoxy-dodeca-3,5,11-triene ( 3 ) have been isolated from the oil of Artemisia pallens. The synthesis of the isomeric mixture is described.