Selective photochemical cleavage of an α-ketoamide in a highly functionalised macrolide ascomycin

A novel photochemical amide cleavage reaction of (6S)-methoxyascomycin opening a pathway for the selective cleavage of the pipecolic acid, is described. The scope of this reaction with several analogues carrying suitable protecting groups is examined.     

Ionic liquids/H2O systems for the reaction of epoxides with NaN3: a new protocol for the synthesis of 2-azidoalcohols

Oxiranes undergo ring opening rapidly with sodium azide in a [bmim]BF₄/H₂O or [bmim]PF₆/H₂O (2:1) solvent system, under mild and neutral reaction conditions to afford the corresponding 2-azidoalcohols in high to quantitative yields. The remarkable features of this procedure are improved yields, enhanced reaction rates, high regioselectivity and ease of recyclability of ionic liquids (ILs). The recovered ionic liquid can be reused for four to five times but with gradual decrease in activity.     

Synthesis of 6-vinyl and 5-vinylproline analogues of ascomycin

6-Vinyl (12) and (5R)- and (5S)-vinylproline (18, 19) analogues of ascomycin are synthesised starting from the known suitably protected (6S)-methoxy-9-hydroxy derivative (4) of ascomycin. The strategy involves hydrolytic cleavage of the C_ε-N bond of the pipecolic acid moiety, extension of the amino acid side chain by two or one carbon units, functional group manipulations, Pd-catalysed reinstallation of the C_ε-N or C_δ-N bonds, followed by deprotection and oxidation.     

Extraction of thorium(IV) as perchlorate and chloroacetate complexes with 1-phenyl-2,3-dimethyl-5-pyrazolone (antipyrine)

Summary Thorium was extracted quantitatively with the neutral ligand 1-phenyl-2,3-dimethyl-5-pyrazolone (Apy) in the presence of perchlorate (ClO₄^-) and di/trichloroacetates (DCA/TCA) at pH 2.5 into an organic solvent. Optimization of experimental parameters like pH, equilibration time, solvents, reactant concentrations, best suited conditions for back extraction, interference due to the presence of different anions and cations and effect of metal ion concentration were studied. The composition of the complexes has been established using log-log plots and are represented as [Th(Apy)₂(ClO₄)₄], [Th(Apy)₂(TCA)₄], [Th(Apy)(H₂O)(DCA)₄]. The respective conditional stability constants of the effectively extracted complexes have also been calculated as 9.4±0.03 and 10.4±0.04, respectively . The method has been extended for the separation of thorium from a number of cations in binary and multicomponent mixtures. The method is simple, rapid, selective and has a good reproducibility (±0.5%).     

Field and Frequency Effects in a Nematic Mixture of Negative and Positive Dielectric Anisotropy

The molecular alignment in the nematic liquid crystal mixture of p-ethoxy benzylidene p′-n-butyl aniline (EBBA) and p-ethoxy benzylidene p′-cyano aniline (EBCA) has been investigated by measuring the dielectric constant at 1 MHz. Detailed investigation has been carried out for a composition of 2.74%, of EBCA in EBBA for different electric and magnetic field strengths and at different frequencies of the applied electric field. Both parallel and perpendicular electric and magnetic field configurations have been employed. Temperature and frequency dependence of the dielectric anisotropy have been studied.

Two interesting features have been observed. I) In the crossed field configuration complete molecular alignment could be observed by suitably changing the electric field strength. The range of electric field strength required to change the molecular ordering, is frequency dependent. This range shows a minimum in the neighbourhood of 2 kHz. 2) It has also been observed that in the parallel field configuration minimum dielectric constant change is observed apparently independent of frequency and electric field strength. Detailed results of the field and frequency effects and of optical studies in this mixture are reported.     

Oligosaccharide Analogues of Polysaccharides,Part 21 , Towards New Cellulose I Mimics: Synthesis of Dialkynyl C‐glucosides of peri‐Substituted Anthraquinone

The bis‐C‐glucoside 2 has been synthesised as the first representative of a series of templated glucosides and cellooligosaccharides that mimick part of the unit cell of cellulose I. As expected, there are, at best, weakly persistent H‐bonds between the two glucosyl residues in (D₆)DMSO and (D₇)DMF solution. The acetylated oct‐1‐ynitol 7 and deca‐1,3‐diynitol 12 were prepared from the gluconolactone 5 (Scheme 1). Coupling of 12 to PhI and 2‐iodothiophene yielded 13 and 14 , respectively, while dimerisation of the benzylated and acetylated deca‐1,3‐diynitols 10 and 12 afforded the bis‐C‐glucosyloctatetrayne 15 and the less stable 16 , respectively. The 2‐glucosylthiophene 17 was obtained by treating the C‐silylated deca‐1,3‐diynitol 9 with Na₂S. Cross‐coupling of (trimethylsilyl)acetylene (TMSA) with 1,8‐bis(triflyloxy)‐9,10‐anthraquinone ( 20 ) at elevated temperature gave the dialkynylated 21 ; its structure was established by X‐ray analysis (Scheme 2). Sequential coupling of 6 or 7 and TMSA to 20 gave the symmetric dialkyne 21 , the mixed dialkynes 23 (from 6 ) and 25 (from 7 ), and the symmetric diglucoside 36 (from 7 ) in modest yields; a stepwise coupling to the acetylated monotriflate 28 proved advantageous. It led to the oct‐1‐ynitol 29 and the deca‐1,3‐diynitol 33 that were transformed into the triflates 30 and 34 , respectively. Coupling of the triflate 34 to the oct‐1‐ynitol 7 gave the unsymmetric bis‐C‐glucoside 35 ; this was obtained in higher yields by coupling the triflate 30 to the deca‐1,3‐diynitol 12 . Coupling of the bistriflate 20 with either 7 or 12 afforded the symmetric bis‐C‐glucosides 36 and 37 , respectively. Deacetylation (KCN in MeOH) of 35 – 37 provided the unsymmetric bis‐C‐glucoside 2 and the symmetric analogues 3 and 4 .     

Efficient algorithms for Koblitz curves over fields of characteristic three

The nonadjacent form method of Koblitz [Advances in Cryptology (CRYPTO'98), in: Lecture Notes in Comput. Sci., vol. 1462, 1998, pp. 327–337] is an efficient algorithm for point multiplication on a family of supersingular curves over a finite field of characteristic 3. In this paper, a further discussion of the method is given. A window nonadjacent form method is proposed and its validity is proved. Efficient reduction and pre-computations are given. Analysis shows that more than 30% of saving can be achieved.     

Effective equidistribution of eigenvalues of Hecke operators

In 1997, Serre proved an equidistribution theorem for eigenvalues of Hecke operators on the space S(N,k) of cusp forms of weight k and level N. In this paper, we derive an effective version of Serre's theorem. As a consequence, we estimate, for a given d and prime p coprime to N, the number of eigenvalues of the pth Hecke operator Tp acting on S(N,k) of degree less than or equal to d. This allows us to determine an effectively computable constant Bd such that if J₀(N) is isogenous to a product of Q-simple abelian varieties of dimensions less than or equal to d, then N?Bd. We also study the effective equidistribution of eigenvalues of Frobenius acting on a family of curves over a fixed finite field as well as the eigenvalue distribution of adjacency matrices of families of regular graphs. These results are derived from a general “all-purpose” equidistribution theorem.     

In situ nucleophilic substitution reaction of N,N-dialkylaminoethyl-2-chlorides monitored by gas chromatography/mass spectrometry

The detection and identification of degradation products of scheduled chemicals, which are characteristic markers of Chemical Warfare agents (CWAs), plays a key role in verification analysis. Identification of such non-scheduled but specific markers of CWAs helps in deciphering the kind of agent that was present in the sample submitted for off-site analysis. This paper describes the stability of N,N-dialkylaminoethyl-2-chlorides, which are precursors for highly toxic chemicals like VX, in different solvents. These compounds are stable in chloroform, acetonitrile, hexane and dichloromethane but tend to undergo in situ nucleophilic substitution reaction in the presence of alcohols giving the corresponding alkyl ether. The study shows that N,N-dialkylaminoethyl alkyl ethers can be used as markers of N,N-dialkylaminoethyl-2-chlorides. A detailed degradation study of these compounds in the presence of alcohols was carried out and it was found that the reaction follows pseudo-first order kinetics. Electron ionization mass spectral data for the methyl ethers of all the compounds are briefly discussed.