Electrochemical transfer of [18F]fluoride from [18O]water into organic solvents ready for labeling reactions

For labeling reactions [¹⁸F]fluoride has to be separated from [¹⁸O]water and transferred into an organic solvent suitable for nucleophilic substitutions. An electrolytical method is described for depositing [¹⁸F]fluoride on a vitreous carbon electrode and releasing it directly into CH₃CN or DMSO. In the presence of Et₃N×3HF, [¹⁸F]fluoride is almost quantitatively released into acetonitrile. When using n.c.a conditions, i.e., Et₃N^.HCl, desorption of the ¹⁸F activity is almost 70% and 60% in acetonitrile and DMSO, respectively, already within 5 minutes.     

Efficient synthesis of [2'-18O]uridine and its incorporation into oligonucleotides: a new tool for mechanistic study of nucleotidyl transfer reactions by isotope effect analysis

Lack of sufficient quantities of isotopically labeled materials has precluded the use of heavy atom isotope effects to investigate mechanisms of nucleotidyl transfer reactions in nucleic acids. Here we achieve regioselective opening of 2,2'-cyclouridine with [(18)O2]benzoic acid/potassium hydride, allowing an efficient "one-pot" synthesis of [2'-18O]uridine in 88% yield. Conversion to the corresponding phosphoramidite enables solid-phase synthesis of [2'-(18)O] RNA substrates for isotope effect studies with nucleotidyl transferases and hydrolases.     

Synthesis of O,O-dialkyl S-lupinane thiophosphates,O, O-dialkyl S-epilupinane thiophosphates,and their methiodides

Conclusions We synthesized a number of O,O-dialkyl S-epilupinane thiophosphates, O,O-dialkyl S-lupinane thiophosphates, and their methiodides.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 480–482, February, 1978.     

Oxyfluorotitanophosphate cluster [Ti10P4O16F44]16-: synthesis and characterization of K16[Ti10P4O16F44

One oxyfluorotitanophosphate cluster compound, K16[Ti10P4O16F44], has been synthesized and structurally characterized. As far as we know, it is the first cluster compound for titanophosphate.     

[18F]FDG synthesis by Anatech RB-86 robotic system: Improvements and general considerations

A series of changes and updatings to the [¹⁸F]FDG setup of the Anatech RB-86 robotic system are described. They include improved [¹⁸O]H₂O recovery, “one-pot” reaction, elimination of the SPE step and base-assisted hydrolysis. Considerations on this last point are also reported. Thus, a remarkable improvement in the radiochemical yield, which is now 81% (decay corrected to SOS) with a synthesis time of just 40 minutes, has been achieved. The influence of several different reaction vessel materials on the synthesis is also briefly examined.     

A simple synthesis of a doubly-bridged [16]annulene

Reductive coupling of cychoheptatriene-1,6-dialdehyde using a low-valent titanium reagent provides a one-step route to a paratropic bismethano [16] annulene.     

Synthesis and isomerization of O,O-dialkyl-O-thioglycidyl thiophosphates

Conclusions O,O-Dialkyl-O-thioglycidylthione phosphates obtained by the reaction of O,O-dialkylglycidyl thiophosphates with the ammonium or triethylanmonium salts of dialkylthiophosphoric acids undergo isomerization to give O,O-dialkyl-S-thioglycidylthiol phosphates by the action of both the initial salts and the salts formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2363–2366, October, 1982.     

Energies of charge transfer and supramolecular interactions of some mono O-substituted calix[6]arenes with [60]fullerene by absorption spectrometric method

Equilibria for the formation of supramolecular complexes of [60]fullerene with a series of mono O-substituted calix[6]arenes, namely: (i) 37-methoxy-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (1), (ii) 37-allyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (2), (iii) 37-phenacyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (3), (iv) 37-ethylester-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (4) and (v) 37-benzyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (5) have been studied in CCl4 medium by absorption spectroscopic technique. The stoichiometry has been found to be 1:1 ([60]fullerene:calix[6]arene) in each case. An absorption band due to charge transfer (CT) transition is observed in each case in the visible region. The vertical ionisation potentials (I(D)(v)) of all the calix[6]arenes under study have been estimated utilising CT transition energy. The experimental I(D)(v) values also yield a good estimate of the electron affinity of [60]fullerene. The degrees of CT in the ground state of the complexes have been found to be very low (about 0.15%). Resonance energy of the complexes have been estimated. Thermodynamic parameters for the supramolecular complex formation of [60]fullerene with mono O-substituted calix[6]arene receptors are reported. It is observed that among the calix[6]arenes under the present study, only 1 and 4 form inclusion complexes with [60]fullerene. This has also been substantiated by theoretical calculation using PM3 method. Thus presence of one substituent group (of different types) on the lower rim of the calix[6]arene molecule has been shown to govern the host-guest complexation process.     

The synthesis of methano-bridged bisdehydro [18]-, -[20]-, -[22]-, and -[24] annulenes

Title annulenes were synthesized by Wittig reaction of cyclohepta-1,3,5-triene-1,6-dialdehyde or its vinylogous dialdehydes with 5-methylpenten-2-yn-4-yltriphenylphosphonium bromide, followed by intramolecular oxidative couplings of the resulting acyclic compounds, and they proved to be diatropic or paratropic, corresponding to the number of peripheral π-electrons.     

Ruthenium complexes of thiocinnamaldehydes: synthesis, structure, and [4+2]-cycloaddition reactions

Ruthenium hydrogensulfido complexes [CpRu(P-P)(SH)] ((P-P)=Ph(2)PCH(2)PPh(2) (dppm), Ph(2)PC(2)H(4)PPh(2) (dppe)) were obtained from the corresponding chloro complexes by Cl/SH exchange. Condensation with a range of cinnamaldehydes gave thiocinnamaldehyde complexes [CpRu(P-P)(S=CH-CR(2)=CHR(1))]PF(6) (R(1)=C(6)H(4)X, R(2)=H, Me, X=H, OMe, NMe(2), Cl, NO(2)) as highly-colored crystalline compounds. The thiocinnamaldehyde complexes undergo [4+2]-cycloaddition reactions with vinyl ethers CH(2)=CHOR(3) (R(3)=Et, Bu) and styrenes H(2)C=CHC(6)H(4)Y (Y=H, Me, OMe, Cl, Br, NO(2)) to give complexes of 2,4,5-trisubstituted 3,4-dihydro-2H-thiopyrans as mixtures of two diastereoisomers. The rate of addition of para-substituted styrenes H(2)C=CHC(6)H(4)Y to [CpRu(dppm)(S=CH-CH=CHPh)]PF(6) increases in the series Y=NO(2), Br, Cl, H, Me, OMe, indicating that the cycloaddition is dominated by the HOMO(dienophile)-LUMO(diene) interaction. The strained dienophiles norbornadiene and norbornene also add, giving ruthenium complexes of 3-thia-tricyclo[6.2.1.0(2,7)]undeca-4,9-dienes and 3-thia-tricyclo[6.2.1.0(2,7)]undec-4-enes, respectively. Addition reactions with acrolein, methacrolein, methyl vinyl ketone, acrylic ester, or ethyl propiolate finally yielded ruthenium complexes of 3,4-disubstituted 3,4-dihydro-2H-thiopyrans and 4H-thiopyrans, respectively.     

Single neutron transfer reactions in the systems:139La+16O,93Nb+12C,14N,16O and20Ne

Data from the quasi-elastic transfer reaction products¹⁴⁰La and^92mNb exhibit near zero effective ranges, flat excitation functions over large energy ranges and Q independent yields. These features are used to characterise quasi elastic reactions via the target-like product.     

Functionalized polyolefin synthesis using [P,O]Ni catalysts

Nickel olefin polymerisation catalysts containing bulky phosphino-enolate ligands are shown to give methyl methacrylate end-functionalized polyolefins.     

Computational study on the electrocyclic reactions of [16]annulene

The electrocyclic reactions of [16]annulene have been investigated by ab initio and DFT calculations. Among the six conformers of [16]annulene identified, 3, with Cs symmetry, is taken as the starting reactant for the cyclization reactions of [16]annulene, even though it is 31.4 kJ mol(-1) less stable than the most stable conformer, 1. The pathways of the electrocyclic reactions from reactant 3 to two tricyclic products, 5 and 6, have been found. All pathways identified are stepwise, i.e., the two ring closure processes occur one after the other. Among the pathways found, the ones with the lowest overall barrier for reactions 3 --> 5 and 3 --> 6 have the same rate-determining step and hence the same overall barrier, 131.0 kJ mol(-1). Thus, based on the barriers calculated, it is not possible to determine whether 5 or 6 is the dominant product in the cyclization reaction of 3.