Exploring the Synthesis of a New Group of Chiral Ammonium Salts with Specific Configurations at the Stereogenic Nitrogen Centers

A group of new chiral dications with a fixed, specific configuration at the stereogenic nitrogen center was created. Stereoselective synthesis and recrystallization give the diastereomerically and enantiomerically pure dications, including a chiral amphiphile with surface‐active properties.     

Improved determination of the bisphosphonate pamidronate disodium in plasma and urine by pre-column derivatization with fluorescamine, high-performance liquid chromatography and fluorescence detection.

An improved method for the determination of 1-hydroxy-3-aminopropylidene-1,1-bisphosphonate (pamidronate) in human urine and plasma is described. The procedure is based on a co-precipitation of the bisphosphonates (pamidronate and 6-amino-1-hydroxypentilidene-bisphosphonate, used as internal standard) with calcium phosphate. After centrifugation the precipitate is redissolved in hydrochloric acid, followed by a second precipitation. Then the bisphosphonates are dissolved in ethylenediaminetetraacetic acid, derivatized with fluorescamine, and separated by high-performance liquid chromatography. Using fluorescence detection, the limit of quantitation for pamidronate was 0.8 mumol/l in plasma and 0.7 mumol/l in urine.     

Über cyclische Guanidin—Mesityloxid- und Guanidin—Phoron-Kondensate

The basic product synthesized byTraube andSchwarz from mesityl oxide and guanidine has not been 4.4.6-trimethyl-4.5-dihydro-2-pyrimidinamine (1), but a mixture containing the 4.4.6-trimethyl-3.4-dihydro-2(1H)-pyrimidinimine (resp. an isomeric pyrimidinamine)2 a (resp.2 b, 2 c) and the dimeric 4.4′-methylenedi[2(1H)-pyrimidinimine] (resp. an isomeric methylenedipyrimidinamine)3 a (resp.3 b, 2 c) and the dimerisation reaction were studied in a series of experiments. The product of the reaction of guanidine and phorone is not the guanidinopropylpyrimidine8 ⁴, but the 4.4′-spirobi[2(1H)-pyrimidinimine] (resp. a spirobipyrimidinamine)11 a (resp.11 b, 11 c). No determination was possible on the basis of NMR whether the condensation products of guanidine—in solutions ofDMSO-d₆—are pyrimidinimines (2 a, 3 a, 11 a) or pyrimidinamines (2 b resp.2 c, 3 b resp.3 c, 11 b resp.11 c) or mixtures of the isomeric compounds. The NMR-and mass spectra of2 a (resp.2 b, 2 c),3 a (resp.3 b, 3 c),11 a (resp.11 b, 11 c) and their derivates are discussed.     

Synthese arylsubstituierter 2-Pyrimidinamine,Dihydro-2-pyrimidinamine und Pyrimido[1,2-a]pyrimidine durch Reaktion von Guanidin mit Chalkonen

4- and 4-methoxy-, 4-hydroxy- and 2-hydroxychalcone4 e,k,f andg, respectively, are transformed by action of guanidine in benzene to yield 4-(4-methoxyphenyl)-6-phenyl-2-pyrimidinamine (6 e=6 k) and hydroxyphenylpyrimidinamines6 f andg, respectively. In contrast, 4- and 4-chlor-, 4-brom- and 4-phenylchalcone4 h,l–n resp. react with guanidine under analogous conditions to give 4,6-diaryl-1,4-dihydro-2-pyrimidinamines5 h,l–n. The bases5 h,l–n also tend to aromatize, but they can be stabilized by transformation into salts5 h,l–n · HCl with hydrochloric acid. Heating of5 n inDMF under atmospheric oxygen yields 4-(4-biphenyl)-6-phenyl-2-pyrimidinamine (6 n). Action of guanidine on 4-nitrochalcone4 o in chloroform affords 2-amino-4-nitrophenyl-6-phenyl-tetrahydro-4-pyrimidinol8 o, which is transformed by hydrochloric acid into 6-nitrophenyl-dihydropyrimidinamine-hydrochloride5 o · HCl. Treating of the latter with sodiummethylat in methanol yields the very stable dihydropyrimidinamine5 o. Action of guanidine on 4-chlor- and 4-bromchalcone4 h andm respectively (in addition to5 h andm) yields 2,4,6,8-tetraaryl-1,4-dihydro-2H-pyrimido[1,2-a]pyrimidines7 h andm, respectively.

Herrn Prof. Dr.Erwin Schauenstein mit den besten Wünschen zum 65. Geburtstag gewidmet.     

Determination of unchanged hydralazine in plasma by gas-liquid chromatography using nitrogen-specific detection

A gas chromatographic method is described for the specific determination of unchanged hydralazine in plasma. On treatment with 2,4-pentanedione, hydralazine is converted into 1-(3,5-dimethyl-1-pyrazolyl)phthalazine, a stable compound which is easily extracted from biological material and determined quantitatively by gas chromatography with nitrogen-specific detection. 4-Methylhydralazine is used as an internal standard. The sensitivity of the method is ca. 10 ng/ml. Hydrazones of hydralazine do not interfere with the assay.     

Conformal fields,restriction properties,degenerate representations and SLEChamps conformes,propriété de restriction,représentations dégénérées et SLE

We relate the Schramm–Loewner Evolution processes (SLE) to highest-weight representations of the Virasoro Algebra. The restriction properties of SLE that have been recently derived in [19] play a crucial role. In this setup, various considerations from conformal field theory can be interpreted and reformulated via SLE. This enables one to make a concrete link between the two-dimensional discrete critical systems from statistical physics and conformal field theory. To cite this article: R. Friedrich, W. Werner, C. R. Acad. Sci. Paris, Ser. I 335 (2002) 947–952.