Preparation and properties of polymers from aryl cyclic sulfonium zwitterions

A new class of zwitterionic monomers were prepared in which the positive and negative sites are cyclic sulfonium and phenolate. Thermal polymerization occurs by phenolic anionic attack upon the aliphatic carbon α to the sulfonium sulfur. Polymerization proceeds with ring opening and net loss of charge to form nonionic polymers. The monomeric zwitterions are generally hydrated, crystalline solids that are soluble in water or alcohol. Chlorination of the aromatic portion of the molecule yields nonhydrated species. The polymerizations of 1-(4-hydroxy-3-methylphenyl)tetrahydrothiophenium hydroxide inner salt (dihydrate) and 1-(3,5-dichloro-4-hydroxyphenyl)tetrahydrothiophenium hydroxide inner salt were studied. The latter monomer gave a polymer with M?_n of 46,000 when a nucleophile was present as an initiator. The physical properties of this polymer were determined. Cyclization appears to be the main mechanism of termination in the polymerization of zwitterions.     

LiTiCl3: Synthesis and thermal behaviour

LiTiCl₃ is obtained as one example within an ample solid solution, Li_24–2nTi_nCl₂₄ (?4?n?10), by synpropotionation of TiCl₃ and Ti in the presence of LiCl (2:1:3 molar ratio) in sealed tantalum tubes at 750°C. It crystallizes with the inverse spinel-type structure according to (Li_0.67)^[4](Li_0.67Ti_1.33)^[4]Cl₄ with, at 25°C, a = 1048.62(4) pm, space group Fd3m. Thermal expansion is linear with α = 4.85 × 10^?5K^?1 up to about 300°C and thereafter, when the migration of Li⁺ from tetrahedral to octahedral interstices becomes increasingly important, it exhibits a relative decrease resulting, finally, in the phase transition to a NaCl-type structure that is observed for the first time at about 575°C.     

A novel synthesis of substituted 4H-pyrazolo[3,4-d]pyrimidin-4-ones

A novel synthesis of 4H-pyrazolo-[3,4-d]pyrimidin-4-ones is described. This approach utilizes an in situ generated iminochloride as a key precursor for amidine formation, with subsequent base-catalyzed ring closure. This method represents a mild and efficient entry into this ring system which is amenable to diversification of the core template.     

Chlor-dimethylaminosulfonium-Salze Darstellung und IR-Spektren

Chloro-dimethylaminosulfonium Salts. Preparation and I. R. Spectra By reaction of bis-dimethylamino-mono- resp. -disulfane with a mixture of chlorine/antimony(V) chloride the chloro dimethylaminosulfonium hexachloroantimonates(V) [(CH₃)₂N]₂SCI^⊕SbCl₆^? (I) and (CH₃)₂NSCI₂^⊕SbCl₆^? (II) are yielded. The i. r. spectra of these compounds were measured and assigned.     

Acyl- und Alkylidenphosphane. XXII [1]. Synthese und Struktur des 1, 3-Dimethyl-2,2,4,4-tetrakis-(trimethylsilylsulfano)-1,3-diphosphetans

Acyl- and Alkylidenephosphines. XXII. Synthesis and Structure of 1, 3-Dimethyl-2,2,4,4-tetrakis(trimethylsilylsulfano)-1,3-diphosphetane At ?30°C methylbis(trimethylsilyl)phosphine reacts with carbon disulfide to give a red adduct first which rearranges to [bis(trimethylsilylsulfano)methylidene]methylphosphine 1a . In contrast to the thermally stable phenyl derivative 1b [2], this compound with its insufficiently shielded P?C group dimerizes fast with increasing temperature. 1,3-Dimethyl-2,2,4,4-tetrakis(trimethylsilylsulfano)-1,3-diphosphetane 2a formed by this reaction, crystallizes in the triclinic space group P1 with following dimensions of the unit cell, determined at a temperature of measurement of ?80 ± 3°C: a = 1024.7(3); b = 1360.2(5); c = 1326.3(6)pm; α = 117.85(4); ß = 111.05(3); γ = 72.09(3)°; Z = 2. Due to ring folding at the P1? P2 axis of 149.1°, the molecule shows pseudosymmetry C_s. Characteristic averaged bond lengths and angles obtained at an R_w-value of 0.030, are: P? C(endocyclic) 188 and 191; P? CH₃ 184; C? S 183; S? Si 216 pm; C? P? CH₃ 105; P? C? S 113; S? C? S 114; C? S? Si 108; P? C? P 90 and C? P? C 86°.     

Solid-solute phase equilibria in aqueous solution. VI. Solubilities,complex formation,and ion-interaction parameters for the system Na+−Mg2+−ClO 4 − −CO2−H2O at 25°C

The stoichiometric solubility constant of eitelite (NaMg _0.5 CO ₃ +2H⁺ ⇄ Na⁺+0.5Mg ²⁺ +CO ₂ (g)+H ₂ O, log^*K _pso ^I =14.67±0.03 was determined at I=3 m (mol kg⁻¹) (NaClO ₄ ) and 25°C. The stability of magnesium (hydrogen-)carbonato complexes in this ionic medium was explicitely taken into account. Consequently, trace activity coefficients of free ionic species, calculated from the Pitzer model with ion-interaction parameters from the literature, were sufficient for an evaluation of the thermodynamic solubility constants and Gibbs energies of formation for eitelite (−1039.88±0.60), magnesite (−1033.60±0.40), hydromagnesite (−1174.30±0.50), nesquehonite (−1724.67±0.40), and brucite (−835.90±0.80 kJ-mol ⁻¹ ). The increasing solubilities of nesquehonite and eitelite at higher sodium carbonate molalities were explained by invoking a magnesium dicarbonato complex (Mg²⁺+2CO ₃ ²⁻ ⇄ Mg(CO₃) ₂ ²⁻ , log β_z = 3.90 ± 0.08). A set of ion-interaction parameters was obtained from solubility and dissociation constants for carbonic acid in 1 to 3.5 m NaClO ₄ media which reproduce these constants to 0.02 units in log K. The following Pitzer parameters are consistent with the previously studied formation of magnesium (hydrogen-)carbonato complexes in 3m NaClO ₄ . The model and Gibbs functions of solid phases derived here reproduce original solubility data (−log [H⁺], [Mg ²⁺ ] _tot ) measured in perchlorate medium within experimental uncertainty. Presented at the XXII International Conference on Solution Chemistry, July 14–19, 1991, Linz, Austria.     

Salvinicins A and B, new neoclerodane diterpenes from Salvia divinorum

[reaction: see text] Two new neoclerodane diterpenes, salvinicins A (4) and B (5), were isolated from the dried leaves of Salvia divinorum. The structures of these compounds were elucidated by spectroscopic techniques, including (1)H and (13)C NMR, NOESY, HMQC, and HMBC. The absolute stereochemistry of these compounds was assigned on the basis of single-crystal X-ray crystallographic analysis of salvinicin A (4) and a 3,4-dichlorobenzoate derivative of salvinorin B.     

Two types of intramolecular addition of an Al-N multiple-bonded monomer LAlNAr' arising from the reaction of LAl with N3Ar' (L = HC[(CMe)(NAr)]2, Ar' = 2,6-Ar2C6H3, Ar = 2,6-iPr2C6H3)

The reaction of beta-diketiminated aluminum(I) monomer LAl with a large bulky azide N3Ar' (L = HC(CMeNAr)2, Ar' = 2,6-Ar2C6H3, Ar = 2,6-iPr2C6H3) in the temperature range from -78 degrees C to room temperature affords two different isomers 2 and 3, which have been characterized by spectroscopic and X-ray structural analyses, as well as elemental analysis. The variable-temperature 1H NMR kinetic studies of this reaction indicate the existence of the monomer LAlNAr' (1) at low temperature and the thermal stability of the compounds increases in the order of 1 < 2 < 3.     

Access to the structures of fluoromagnesium compounds: synthesis and structural characterization of the β-diketiminato magnesium fluoride [{CH(CMeNAr)2}Mg(μ-F)(THF)]2·toluene

β-Diketiminato magnesium fluoride [{CH(CMeNAr)₂}Mg(μ-F)(THF)]₂·toluene (Ar=2,6-i-Pr₂C₆H₃, 2·toluene) was synthesized. The molecular structure of 2 revealed for the first time, the double fluoro bridge feature between the two magnesium atoms with a typical MgF bond length (average 1.95 Å).     

Zur Struktur zweier Arsen- und Antimontricarboxylate

Zusammenfassung Arsen-tris(2,2-dimethylpropionat) (1) kristallisiert monoklin in der Raumgruppe P2₁/n mita=926.2,b=2158.6,c=983.7 pm, =94.92° undZ=4. As hat gegenüber O die Koordinationszahl 3+3. Antimontripropionat (2) kristallisiert monoklin in der Raumgruppe P2₁/c mita=930.2,b=863.0,c=1575.2 pm, =90.27 undZ=4. Die Moleküle sind intermolekular zu Ketten verknüpft, wodurch Sb die Koordinationszahl 3+3 (+3) erreicht.

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Structure of arsen(III) and antimony(III) carboxylates

Summary Arsen-tris(2,2-dimethylpropionate) (1) crystallizes monoclinic in the space group P2₁/n witha=926.2,b=2158.6,c=983.7 pm, =94.92°, andZ=4. As has a coordination number of 3+3. Antimony tripropionate (2) crystallizes monoclinic in the space group P2₁/c witha=930.2,b=863.0,c=1575.2 pm, =90.27, andZ=4. The molecules are bridged to chains; therefore, Sb reaches the coordination number 3+3 (+3).