Structural study of the 1:1 clathrate of an asymmetric calix[4]arene and acetone

The crystal and molecular structure of the 1:1 clathrate of the asymmetric calix[4]arene,1, and acetone has been determined by X-ray analysis. The crystal data are: tetragonal, space groupP4/n,a=b=12.574(6),c=12.572(6) Å,V=1988(2) ų,Z=2,D _x =1.111 g cm^–3,D _m =1.108 g cm^–3. Least-squares refinement based on 1131 observed reflections withF ₀>3(F ₀) and anisotropic temperature factors led toR=0.096. In spite of the molecular asymmetric calixarene1 the crystal structure has high symmetry, because a part of the host and guest molecules are in disordered states.     

Spectrophotometric study of acid-base equilibria of 4-(2-benzothiazolylazo)resorcinol and 4-(2-benzothiazolylazo)salicylic acid in water-organic solvent media

The visible absorption spectra of 4-(2-benzothiazolylazo)resorcinol (BTAR) and 4-(2-benzothiazolylazo)salicylic acid (BTAS) have been recorded in water-organic solvent mixtures in the pH range 0.5–12.0. The organic solvents used are methanol, ethanol,n-propanol, iso-propanol, acetone, dioxane and dimethyl formamide. The spectral changes have been explained in terms of shifts in equilibria among different molecular and ionic species of BTAR and BTAS existing in solution. The pK _a values corresponding to the different ionization steps have been determined at 25°C and I=0.1M (KNO₃) by graphic analysis of the absorbance-pH curves. The results obtained are discussed in terms of the molecular structure of the reagents and the nature of the organic co-solvent used.     

Acidity function scale for H2SO4 solutions in phenol-acetone solvents with low water content at 25°C

The indicator method was employed to measure the acidity function H ₀ ^S of H₂SO₄ solutions in solvents consisting of an equimolar mixture of phenol and acetone with 0.8% water (from 3.6·10^–4 to 2.6·10^–2 M H₂SO₄) and 2.5% water (from 4.3·10^–4 to 0.32 M H₂SO₄) and of phenol and acetone in a molar ratio of 1:1.5 with 0.67% water (from 1.63·10^–4 to 7.77·10^–2 M H₂SO₄) and 2.09% water (from 4.49·10^–4 to 0.35 M H₂SO₄) at 25°C. The indicators employed were 4- and 2-nitroaniline.Deceased.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Lenneftekhim Scientific-Commercial Association, St. Petersburg. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 72–78, January, 1992.     

Syntheses of Heterocycles from the Sodium Salts of 3-(1-Adamantyl)-1-hydroxy-1-propen-3-one and 4-(1-Adamantyl)-1-hydroxy-1-buten-3-one

The interaction of the sodium salts of 3-(1-adamantyl)-1-hydroxy-1-propen-3-one and 4-(1-adamantyl)-1-hydroxy-1-buten-3-one with hydroxylamine, hydrazine, and guanidine leads to the synthesis of 5-(1-adamantyl)-5-hydroxy- and 5-(1-adamantylmethyl)-5-hydroxy-2-isoxazolines, 3-(1-adamantyl)- and 3-(1-adamantylmethyl)pyrazoles, 3-(1-adamantyl)-2-phenylpyrazole, and 4-(1-adamantyl)-2-amino- and 4-(1-adamantylmethyl)-2-aminopyrimidines.     

Reactions of 9,10-phenanthrenequinone and its nitro derivatives with acetone in the presence of Al2O3

The addition of acetone to 9,10-phenanthrenequinone and 2-nitro-, 2,7-dinitro-, and 2,4,7-trinitro-9,10-phenanthrenequinones in the presence of Al₂O₃ affords mono- and bisadducts. The crystal structures of 10-hydroxy-10-(2-oxopropyl)-2-nitro-9,10-dihydrophenanthren-9-one and 9,10:10,9-bishemiketal of 9,10-dihydroxy-2-nitro-9,10-bis(2-oxopropyl)-9,10-dihydrophenanthrene were determined.     

Reaction of Acetone Cyanohydrin with Thiosemicarbazide

We have established that when acetone cyanohydrin is heated with thiosemicarbazide in aqueous medium, 3-mercapto-6,6-dimethyl-1,2,4-triazin-5-one and 2-methyl-2-thiosemicarbazidopropanoic acid are formed. Cyclization of the latter in dioxane in the presence of H₃BO₃ leads to 2-amino-5,5-dimethyl-1,3,4-thiadiazin-6-one.     

Change of water structure by solvents and polymers

Viscosity measurements have been made of water-solvent and water-polymer solutions in a temperature range of 20–60 centigrades. A medium structure temperatureT ₀ was calculated from the Vogel-equation. Water has a structure temperature of 140–150 K, its decrease indicates structure breakage, an increase structure promotion. Pyridine, dioxane, dimethylformamide and urea are structure breakers. This is explained by a shift of the equilibrium — bonded water molecules — nonbonded — to the right. Acetone shows hydrophobic bonding in the same concentration range of 0–10 mole % as the normal alcohols. They are quasifree liquids-structure temperature zero-in the pure state. This is explained by hydrogen bridged dimer formation with the exception of tert-butanol. Its 3 methylgroups sterically prevent dimer formation and cause structuring. Adding urea to methanol-water solutions breaks water structure according to urea concentration but extends the hydrophobic bonding maximum over the whole diagram. Glucose-water solutions have a minimum in the structure temperature diagram. Its left side indicates waterstructure breakage, its right side formation of a new structure forced upon water by the sugar. The equilibrium can be formulated: Waterlike bonded-nonbonded-hetero (solvent)-like bonded, Ribose also shows this minimum but after a short range of heterobondedness the structure is completely broken to nonbondedness.The polymers dextrane and polyvinylpyrrolidone are strong waterstructure breakers. Dextrane much stronger than PVP, it breaks to nonbondedness while PVP maintains a certain structuring, perhaps indicating heterobonding at higher concentrations. Polyacrylamide is a strong structurebreaker. It resembles urea in this sense. Perhaps the solvationwater structure of the NH₂ groups is very different from pure waterstructure. Polyacrylicacid breaks waterstructure completely, if sodiumchloride is added waterstructure is rebuilt again. The only waterstructure promoting polymer is natural gelatine. Perhaps this structure is different from pure water or the watermolecule equilibrium is shifted towards bondedness. The structure temperatures of pure polyethyleneglycoles show a minimum with increasing molecular weight. The high structure temperature of the small chains is explained by long chain assoziates formation through hydrogen bridging. This liquid of long assoziate chains is structured and has a high structure temperature. With increasing molecular weight ringformation instead of linear assoziation becomes possible. These neutral rings form a free liquid. Long chains again have a linear structure and the structure temperature increases at higher molecular weights. Existence of linear chain assoziation of low molecular PEGs is proved with their breakage by adding the chain terminating methanol.Dedicated to Prof. Dr. F. H. Müller.Herrn Chemotechniker D. Ziegler möchte ich für die sorgfältige Durchführung der Messungen sehr danken.Dem Verband der Chemischen Industrie danke ich sehr für die Ermöglichung der Arbeit.     

Solid-phase microextraction for the analysis of short-chain chlorinated paraffins in water samples

A novel solid-phase microextraction (SPME) method coupled to gas chromatography with electron capture detection (GC-ECD) was developed as an alternative to liquid-liquid and solid-phase extraction for the analysis of short-chain chlorinated paraffins (SCCPs) in water samples. The extraction efficiency of five different commercially available fibres was evaluated and the 100-microm polydimethylsiloxane coating was the most suitable for the absorption of the SCCPs. Optimisation of several SPME parameters, such as extraction time and temperature, ionic strength and desorption time, was performed. Quality parameters were established using Milli-Q, tap water and river water. Linearity ranged between 0.06 and 6 microg l(-1) for spiked Milli-Q water and between 0.6 and 6 microg l(-1) for natural waters. The precision of the SPME-GC-ECD method for the three aqueous matrices was similar and gave relative standard deviations (RSD) between 12 and 14%. The limit of detection (LOD) was 0.02 microg l(-1) for Milli-Q water and 0.3 microg l(-1) for both tap water and river water. The optimised SPME-GC-ECD method was successfully applied to the determination of SCCPs in river water samples.     

Crystal structure of the molecular inclusion complex tetra-p-nitro-tetra-O-butyl calix[4]arene with acetone (1:2)

The crystal structure of the inclusion complex of tetra-p-nitro-tetra-O-butyl calix[4]arene 1 with acetone, [(C₄₄H₅₂N₄O₁₂)·2CH₃COCH₃], was measured by X-ray crystallographic analysis with an imaging plate method. It belongs to the space group C2/c, with a = 13.131(3),b = 21.480(4), c = 19.645(4)Å, = 105.69(3)°, and D_cale = 1.177 mg/m³ for Z = 4. Crystal data indicate that the host molecule 1 exist in a pinched-cone conformation, and the action of one molecule of host upon two molecules of acetone forms a channel type intermolecular inclusion complex.     

水杨酸类糖酯化合物的合成及其生物活性

将水杨酸及乙酰水杨酸分别与溴代糖作用, 合成了10个水杨酸类糖酯化合物. 所有化合物经元素分析和1H NMR确认了其结构, 并证明产物为β-构型, 反应具有立体专一性. 生物活性初步测定结果表明, 该类化合物具有一定的诱导活性, 且一些化合物的诱导活性好于水杨酸.