Metallfällungen mit Nitropnenylarsinsäuren

Zusammenfassung Die qualitative Fällung von Metallionen mit den drei isomeren o-, m- und p-Nitrophenylarsinsäuren wird beschrieben und auf Unterschiede der p_h-Werte des Fällungsbeginnes hingewiesen. Die Beeinflussung des Fällungsbeginnes durch die Stellung der Nitrogruppe wird hervorgehoben.

---

Summary The precipitation of metal ions by means ofo-, m-, andp-nitrophenyl arsonic acids is described. The differences of the p_H values of the start of the precipitation are pointed out. The effect of the position of the nitro group on the beginning of the precipitation is stressed.

---

Résumé On décrit la précipitation qualitative d'ions métalliques par les trois isomèreso., m. etp. de l'acide nitrophénylarsonique et l'on donne des indications concernant les différences de valeur du p_h lors du commencement de précipitation. On met en évidence l'influence de la position du groupe nitro sur le commencement de précipitation.

     

Application of multiparameter equations to calculation of the mutual solubility in water-organic solvent binary systems

The solubility of organic liquids in water and of water in organic liquids is primarily determined by the capability of organic liquids for hydrogen bonding. Adequate generalization of the solubility data is possible only with multiparameter equations taking also into account other properties of organic components, including the cohesion and molar volume.     

Total synthesis of the marine alkaloid halitulin

The structure of the strongly cytotoxic marine alkaloid halitulin (1) has been confirmed by total synthesis and its absolute configuration determined as (15S). The synthesis follows a strategy previously reported by one of us and uses an efficient preparation of the quinoline-7,8-diol unit by modified Baeyer-Villiger and Skraup reactions. The O-benzyl protecting groups were removed in the last step of the synthesis by transfer hydrogenolysis without concomitant reduction of the quinoline ring. The method can be applied for the synthesis of halitulin analogues.     

Spreading of liquid drops over saturated porous layers

Spreading of small liquid drops over thin porous layers saturated with the same liquid is investigated from both theoretical and experimental points of view. A theory is presented that shows that spreading is governed by the same power law as in the case of spreading over a dry solid substrate. The Brinkman's equations are used to model the liquid flow inside the porous substrate. An equation of the drop spreading is deduced, which shows that both an effective lubrication and the liquid exchange between the drop and the porous substrates are equally important. The presence of these two phenomena removes the well-known singularity at the moving three-phase contact line. Matching of the drop profile in the vicinity of the three-phase contact line with the main spherical part of the drop gives the possibility to calculate the pre-exponential factor in the spreading law via permeability and effective viscosity of the liquid in the porous layer. Unfortunately, the latter dependency turns out to be very weak. Spreading of silicone oils over different microfiltration membranes is carried out. Radii of spreading on time experimental dependencies confirm the theory predictions. Experimentally found coefficients agree with theoretical estimations.     

Reaction of 2,3,3-trimethyl-3H-indole hydrochloride with methacrylic and crotonic amides

Reaction of 2,3,3-trimethyl-and 2,3,3,5-tetramethyl-3H-indole hydrochlorides with methacrylic and crotonic amides gives 3- and 4-methyl-1,2,3,4,10,10a-hexahydropyrimido[1,2-a]indol-2-ones. With perchloric acid these are converted to 1-carbamoylpropyl-3H-indolium perchlorates. The syntheses of 10a-(4-dimethylaminostyryl)- and 10a-[(4-dimethylaminophenyl)butadienyl]-3,10,10-trimethylpyrimido[1,2-a]indol-2-ones have been studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 625–627, May, 1990.     

Novel annulene dications from methylated [2.2]metacyclophane monoenes and [e]-ring benzannelated dimethyldihydropyrene

Tetramethyl- and hexamethyl-substituted [2.2]metacyclophane monoenes (10 and 11) are transformed into their corresponding trans-dimethyldihydroethanophenanthrenium dications (14(2+) and 15(2+)) in FSO(3)H x SbF(5) (4:1) and FSO(3)H x SbF(5) (1:1) with SO(2)ClF or SO(2) as the solvent; these 10 pi-dications are equivalent to the C-4/C-5 diprotonated dications of the 2,7-dimethyl derivative of trans-DMDHP, 3a. The trans-12c,12d-dimethyl-12c,12d-dihydrobenzo[e]pyrene (6) reacts with FSO(3)H/SO(2)ClF under surprisingly mild conditions to give initially a persistent diprotonated dication (6H(2)(2+)) and, subsequently, the oxidation dication (6(2+)); the 6(2+):6H(2)(2+) ratio reaches 4:1 after 1 week at low temperature. Protonation of the anti-metacyclophane (13) was also examined. Charge delocalization mode and tropicity in the resulting dications are gauged via detailed NMR studies at 500 MHz.     

Instrumental neutron activation analysis of tree rings for dendrochemical studies

Instrumental neutron activation analysis (INAA) was employed to determine zinc, cadmium and potassium concentrations in the growth rings of ponderosa pine (Pinus ponderosa Dougl.) trees growing along the shores of Lake Roosevelt in Washington State, U.S.A. where mineral processing activities have resulted in high burdens of zinc and cadmium in the lake sediments. The tree growing along the contaminated waterway display elevated concentrations of zinc in its growth rings relative to a tree growing along an uncontaminated tributary of Lake Roosevelt. Cadmium concentrations in the growth rings from both sites are similar from 1988 to 1993. Water quality data indicate an increased concentration of cadmium in the lake from 1984 to 1988. The increased concentrations of cadmium in the lake water were reflected in apparent increases in concentrations of cadmium in individual rings of the tree sampled at the contaminated site. This suggests that translocation of cadmium in the sapwood of heartwood-forming species does not occur in the short term, and thus may not be a limiting factor in using trees as environmental monitors for cadmium. In addition, five-year tree ring segments were analyzed and subsequently reanalyzed as individual single-year ring segments. The analytical data obtained for the pooled individual rings are essentially the same as for the five-year segments, demonstrating the utility of NAA for dendrochemical studies.     

Asymmetric nitrogen—41: Stereochemistry of bicyclic 1,2-cis-diaziridines

The twisting of 5- and 6-membered rings in bicyclic cis-diaziridines—1,5-diazabicyclo [3.1.0]hexanes 12–17 and l,6-diazabicyclo[4.1.0]heptane 18—is a rapid process in the time scale of ¹H- and ¹³C-NMR even at -80°. According to the ¹H- and ¹³C-NMR spectra, 1,5-diazabicyclo [3.1.0]hexanes 12,13,15a,15b and 16a,16b do, exist mostly in the boat form ; only the introduction of endo substituents into position 3 or 6 leads to the population of the chair, as is the case with 14 and 17. 2,4-Dialkyl substituted 1,5-diaza- and 1,3,5-triazabicyclo[3.1.0]hexanes are formed via a transition cyclization state similar in its geometry to the initial chair-shaped N-chlorodi(tri)azanes.     

The effect of crown ethers on the alkylation of a cyclic β-keto ester

The effects of crown ethers (6 and 7) on the reactions of sodium (2a) and potassium enolates (2b) of 2-ethoxycarbonylcyclohexanone (1) with isopropyl iodide in dimethylsulfoxide and dimethoxyethane have been investigated. When the addition of crown ether promoted dissociation of ion pair 2 in either of the two solvents, the total rate of reaction (k_t) increased and the ratio of carbon- (3) to oxygen-alkylation (4 and 5) products decreased. The results are consistent with the involvement of both the ion pair and more dissociated species in alkylation and with greater reactivity for the latter.     

Comparative studies of reactions of commercial polymers with molecular oxygen,singlet oxygen,atomic oxygen and ozone—II. Reactions with 1,2-polybutadiene

The oxidations of 1,2-polybutadiene by molecular oxygen, singlet oxygen, atomic oxygen and ozone have been studied using u.v. and i.r. spectroscopic methods. Some possible implications of the results of oxidation in the presence of singlet oxygen (parallel free radical oxidation) and atomic oxygen (formation of NO₂ and its reaction with polymer) are discussed. Crosslinking was observed during all types of oxidation. A new mechanism involving formation of free radicals has been considered in detail. During ozonization of 1,2-polybutadiene, formation of formaldehyde and formic acid were detected. An ozonization mechanism has been proposed.