BASE-SPECIFIC DAMAGE INDUCED BY 4-THIOURIDINE PHOTOSENSITIZATION WITH 334-nm RADIATION IN M13 PHAGE DNA

Abstract— Site-specific DNA damage caused by 334-nm radiation in the presence of the rare Escherichia coli base 4-thiouridine was investigated in vitro by detecting the sites of the termination of DNA synthesis with irradiated M13 phage DNA used as a template. Single-strand breakage was also examined. The results indicate that 334-nm radiation at very low fluences in the presence of 4-thiouridine induces termination of strand synthesis at thymine base sites and at the base immediately prior to thymine. Termination at these sites was diminished by treatment with hot piperidine. Strand cleavage by piperidine treatments was observed preferentially at the guanine site, but only after irradiation at much larger fluences. It is hypothesized that at low fluences 4-thiouridine forms photoadducts with thymine that block DNA synthesis, while at high fluences the guanine site is damaged via oxygen species.     

The product of the condensation of lupininic acid with piperidine

The condensation of lupininic acid with piperidine in the presence of phosphorus pentoxide forms d-epilupin-inoylpiperidine. The reduction of d-epilupininoylpiperidine with lithium aluminum hydride has given piperidino-d- epilupinane.The lupininic acid described in the literature is d-epilupininic acid. So as not to produce confusion, we also call it lupininic acid.     

The Mechanism of Schiff Base Formation of Some Arylidenes-p-Aminosalicylic Acid

Formation of a series of Schiff bases derived from p-aminosalicylic acid I and various aromatic aldehydes has been studied kinetically in ethanol medium in presence of piperidine as a basic catalyst. The order of the reaction is determined to each reactant by following the concentration of the Schiff base formed during the reaction. The reaction is Kinetically third-order in the presence of low concentration of piperidine, first-order to each of I , aldehyde and piperidine. On the other hand, in presence of ≥5×10^?4 M of piperidine the order of the reaction changed to second-order, thus much the reaction is independent of piperidine concentration. The rate determining step is suggested to be the dehydration of the carbinolamine intermediate step 4. Variation in reaction rate constants with the different substituent of the aromatic aldehyde, with substituents of aromatic amine and with the nature of the hydroxylic organic solvents as reaction medium are studied and discussed.     

Interaction between coloured pigments and hindered piperidine/antioxidant combinations in the photo-stabilisation of polypropylene

The complex interaction between coloured pigments, a primary antioxidant and a hindered piperidine compound in the photo-stabilisation of polypropylene has been examined using infra-red absorption spectros-copy. Alone, the pigments offered little photo-protection, their order of efficiency being copper phthalocyananine > chromic oxide > cadmium yellow. In the presence of an antioxidant only an additive effect was observed whereas, in the presence of a hindered piperidine stabiliser, there was powerful synergism. However, in the presence of both antioxidant and hindered piperidine compound the synergistic effects were considerably reduced with two of the pigments, cadmium yellow and chrome green, whereas, with copper phthalocyanine, the synergism was enhanced even further. The results indicate that additive adsorption is important with the first two inorganic pigments whereas, with the latter, the bulky organic ligands inhibit any such interaction. In fact, copper phthalocyanine and a hindered piperidine stabiliser exhibit a highly favourable interaction for photo-stabilisation.     

1-Benzenesulfinyl piperidine/trifluoromethanesulfonic anhydride: a potent combination of shelf-stable reagents for the low-temperature conversion of thioglycosides to glycosyl triflates and for the formation of diverse glycosidic linkages

The combination of 1-benzenesulfinyl piperidine (BSP) and trifluoromethanesulfonic anhydride (Tf(2)O) forms a new, powerful, metal-free thiophile that can readily activate both armed and disarmed thioglycosides, via glycosyl triflates, in a matter of minutes at -60 degrees C in dichloromethane, in the presence of 2,4,6-tri-tert-butylpyrimidine (TTBP). The glycosyl triflates are rapidly and cleanly converted to glycosides, upon treatment with alcohols, in good yield and selectivity.     

Novel products from attempted michael addition to 1-methyl-1,2,5,6-tetrahydropyridine-4-carbonitrile

The reaction of some phenols with the title compound, in the presence of sodium, gives 2-(2-hydroxyaryl_piperidine derivatives. Geometrical isomers have been separated, which differ in having an equatorial (A) or axial (B) cyano group on the piperidine chair (the methyl and aryl groups are equatorial in both forms). The x-ray crystallographic structures of an example of each of A and B are reported and the proton NMR spectra are assigned.     

Synthesis and reactions of 4-(arylhydrazino)coumarins

The interaction of 4-hydroxycoumarin with phenyl-, 2-chlorophenyl- and 4-bromophenyhydrazine hydrochlorides in the presence of triethylamine led in all cases to the corresponding 4-(arylhydrazino)-coumarins and 1-aryl-3-(2-hydroxyphenyl)-2H-pyrazolin-5-ones. 4-(Arylhydrazino)coumarins reacted with 4-chlorobenzaldehyde in the presence of piperidine acetate to give the corresponding 2-aryl-3-(4-chlorophenyl)[1]benzopyrano[4,3-b]pyrazol-4-ones. The reaction of 4-(4-bromophenylhydrazino)-coumarin with 4-chlorobenzaldehyde in the presence of piperidine acetate and an excess of piperidine gave 2-(4-bromophenyl)-5-(4-chlorophenyl)-3-(2-hydroxyphenyl)-4-(piperidinocarbonyl)pyrazole, but the reaction of phenyl- and 4-(2-chlorophenylhydrazino)coumarins with 4-chlorobenzaldehyde gave 1-aryl-5-(4-chlorophenyl)-3-(2-hydroxyphenyl)-4-(1-piperidino)carbonyl-4,5-dihydropyrazoles.     

Synthesis and Transformations of Two Types of 4-Phosphorylated Aldehydes of the Oxazole Series

Available N-(1,2,2,2-tetrachloroethyl)dichloroacetamide selectively reacts with trialkyl phosphites and triphenylphosphine, which was used for preparing polycentered electrophilic agents unusually reacting with piperidine and morpholine in the presence of water to give in high yields 4-dialkoxyphosphoryl- or 4-triphenylphosphonio-substituted oxazole-2-carbaldehydes containing piperidine or morpholine moiety in the 5-position. Their structure was determined by spectroscopy and also by chemical transformations into phenylhydrazones, thiosemicarbazones, aminals, and other functional derivatives of these two types of phosphorus-containing aldehydes of the oxazole series.     

Reaction of α-alkoxyacroleins with acetone cyanohydrin

Conclusions -Alkoxyacroleins add acetone cyanohydrin in the presence of piperidine to give 1-N-piperidino-1-cyano-2-alkoxy-2-propenes, which in the presence of piperidine or on long storage are isomerized to 1-N-piperidino-1-cyano-2-alkoxy-1-propenes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2122–2124, September, 1973.     

An infrared and Raman spectroscopic study of the Hofmann-type complexes and clathrates: M(piperidine)2Ni(CN)4; M(piperidine)2Ni(CN)4·1.5G (M=Cd, Co, Ni or Cu; G=benzene)

New Hofmann-type complexes and clathrates of the forms M(piperidine)₂Ni(CN)₄ and M(piperidine)₂Ni(CN)₄·1.5G (M=Cd, Co, Ni or Cu; G=benzene) were prepared in powder form and their infrared and Raman spectra are reported. The spectral features suggest that these compounds are similar in structure to the Hofmann-type clathrates except for the copper compounds. The complex and clathrate of Cu have different spectral features in comparison with its analogues due to the Jahn-Teller effect.     

Alkylation of 1-(prop-2-ynyl)piperidine with СН-acids in ihe presence of mercury(II) acetate

General regilarities of the reaction of C-nucleophiles with 1-(prop-2-ynyl)piperidine in the presence of mercuty(II) acetate to form mono-and dicarbonyl derivatives of piperidine and bis[3-(piperidin-1-yl)prop-1-ynyl]mercury. Conditions of these reactions were optimized.     

Knoevenagel Condensation of Aldehydes with Meldrum's Acid in Ionic Liquids

The Knoevenagel condensation of Meldrum's acid with aromatic aldehydes proceeded efficiently in the recyclable ionic liquid [bmim]BF₄ at room temperature in the presence of catalytic amounts of piperidine.     

Synthesis of New Plant Growth Regulators,Isomeric 1-(Dimethyloctyl)- and 1-Alkylpiperidinium and -morpholinium Halides by Telomerization of Isoprene with Secondary Amines

The known plant growth regulator, Al'den [1-(3,7-dimethyloctyl)-1-allylpiperidinium bromide], and also 1-(3,7-dimethyloctyl)-1-methylpiperidinium iodide were synthesized by treatment with allyl bromide and methyl iodide, respectively, of exhaustively hydrogenated 1-nerylpiperidine which was obtained by anionic telomerization of isoprene with piperidine. Various quaternary ammonium salts having a terpene sub- stituent with unnatural dimethyloctane skeleton, which effectively stimulate florification of Aster Chinensis L., were prepared by the action of alkyl halides on telomerization products derived from isoprene and piperidine or morpholine in the presence of palladium complexes.     

Effect of H2S on pyridine HDN over Ir, Mo and Ir-Mo/Al2O3 sulfide catalysts

The effect of H₂S on hydrodenitrogenation (HDN) of pyridine over alumina supported Mo, Ir and mixed Ir-Mo sulfide catalysts was studied. The pyridine hydrogenation was inhibited by H₂S on all catalysts, while the cleavage of the C-N bond of intermediate piperidine was facilitated on the Mo and inhibited on the Ir and Ir-Mo catalysts. The promotional offect between Ir and Mo was observed in the piperidine cleavage both in the presence and absence of H₂S.     

Spectrophotometric Determination and Kinetic Studies of Condensation of Aromatic Aldehydes with 7,9‐Dioxo‐6,10‐dioxaspiro[4.5]decane

The condensation reaction rates of 7,9‐dioxo‐6,10‐dioxaspiro[4.5]decane with aromatic aldehydes in chloroform in the presence of piperidine has been investigated spectrophotometrically at 25–50 °C. The reaction follows overall second order kinetics, first order in each of the reactants and zero order with respect to piperidine. The rate of condensation increases with the presence of electron withdrawing groups on the aromatic ring of the aldehyde. From the dependence of the rate constants on temperature, activation parameters have been calculated. Plot of ΔH# versus ΔS# for the reaction gave a good straight line with an isokinetic temperature of 367.55 K. Based on this reaction, determination often aromatic aldehydes in a concentration range of 2.65–69.2 μg/mL is proposed.     

Cyclic Phosphorochloridites and Phosphorochloridates Derived from Bromocalix[4]resorcinolarenes

Reactions of bromocalix[4]resorcinolarenes with PCl₃ and POCl₃ in the presence of triethylamine give the corresponding phosphorochloridito and phosphorochloridato cavitands in good yields. Phosphorochloridito cavitands were converted into phosphoramidito cavitands by treatment with piperidine.     

Anionic Polymerization of Methyl Methacrylate in the Presence of Piperidine

Anionic polymerization of methyl methacrylate (MMA) initiated by lithium tert-butoxide (t-BuOLi) was investigated in different mixtures of benzene and piperidine. The latter compound activates the associated alkoxide, as evidenced by the observed increase in the rate of polymerization, proportional to piperidine concentration and also by the lowering of the overall kinetic order of the polymerization reaction with respect to initial monomer concentration. However, at higher piperidine concentration the rate of the polymer growth significantly decreases after a short period of time; a probable reason for this retardation or termination effect is the decay of active growth centers by a termination reaction with the methacrylate carbonyl group. The molecular weight of the polymer is significantly lowered by even a small addition of piperidine as a result of increased initiator efficiency that leads to a higher absolute concentration of active centers and approaches the theoretical limit given by the stoichiometric ratio of monomer and initiator concentrations. The microstructure of the product is affected by the presence of the polar solvent to a considerably lesser degree than in the case of classical alkylmetal initiators. The isotacticity slowly decreases with piperidine concentration over the whole investigated range. The high stability of the complex active center of growth formed by the alkoxide initiator and also the gradual change in the character of the ionic pair at the end of the growing polymer chain are responsible for the relatively small changes of the microstructure.     

Total Synthesis of (−)‐Himeradine A

(?)‐Himeradine A is a complex lycopodium alkaloid with seven rings and ten stereogenic centers that shows anticancer activity against lymphoma L1210 cells. A total synthesis has been developed that builds off prior work on (+)‐fastigiatine. A 2,4,6‐trisubstitited piperidine ring forms the core of the quinolizidine segment, and was prepared by diastereoselective reduction of a pyridine and classic resolution of an intermediate. The remaining secondary amine was introduced with a catalyst‐controlled Overman rearrangement. The piperidine segment was coupled in a B‐alkyl Suzuki reaction with a bicyclic bromoenone, which was a key intermediate for the synthesis of (+)‐fastigiatine. The final transformation featured a transannular Mannich reaction and cyclization to complete the quinolizidine. Five bonds and four new rings were generated in this one‐pot procedure. (?)‐Himeradine A was prepared in 17 steps in the longest linear sequence.     

Synthesis and Biological Activity of 2-Aryl-4-hydroxy-4-methyl-6-oxocyclohexane-1,3-dicarboxamides

Russian Journal of General Chemistry - The reaction of unsubstituted acetoacetamide with aromatic aldehydes in ethanol in the presence of piperidine gave...     

Equilibres Liquide-vapeur Isothermes De Melanges Binaires, Amine+amine

The authors have measured the vapour pressure of the binary systems, piperidine+n -butylamine, piperidine+dipropylamine, piperidine+N-methyl piperidine, piperidine+N,N-dimethyl amino butane and N-methyl piperidine+n -butylamine. The measurements were carried out using an isoteniscope built by Jose [1]. The vapour pressure, excess Gibbs free energies at 298,15, 303,15, 313,15, 323,15, 333,15, and 325,15 K, are reported for these mixtures. The excess Gibbs free energies have been fitted to Redlich-Kister equation. This revised version was published online in July 2006 with corrections to the Cover Date.