Densities and viscosities for binary mixtures of phenetole with 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol,and 1-decanol at different temperatures

Density (ρ) and viscosity (η) values of the binary mixtures of phenetole+1-pentanol, + 1-hexanol, + 1-heptanol, + 1-octanol, + 1-nonanol, and + 1-decanol over the entire range of mole fraction at 293.15, 298.15, 308.15, and 318.15 K have been measured at atmospheric pressure. The excess molar volume (V^E), viscosity deviations (Δη), and excess Gibbs energy of activation (G*^E) have been calculated from the experimental measurements. These results were fitted to Redlich and Kister polynomial equation to estimate the binary interaction parameters. The viscosity data were correlated with equations of Grunberg and Nissan, Hind et al., Frenkel, and McAllister. While the excess molar volumes of phenetole+1-pentanol, + 1-hexanol are positive, the remaining binary mixtures are negative. The viscosity deviations and excess Gibbs energy of activation are negative for all investigated systems. As the chain length of 1-alkanols increases, both viscosity deviations and excess molar volume values decrease while excess Gibbs energy of activation value increase. The temperature has no effect on excess molar volume, slight effect on excess Gibbs energy of activation, and significant effect on viscosity deviations. The calculated functions have been used to explain the intermolecular interaction between the mixing components.     

Photogeneration and reactivity of 1,n-diphenyl-1,n-azabiradicals

The 1,5-diphenyl-1,5-azapentanediyl biradical Ia was generated by photolysis of 1,2-diphenylazacyclopentane (pyrrolidine 1a). Among the reaction pathways followed by Ia, C-N bond reformation with ring closure was found to be the predominating process, as determined by separate irradiation of either of the pure enantiomers of 1a. Disproportionation was a minor process and took place only via H abstraction by the C5 benzylic radical. Another minor pathway was C5-aryl coupling, with formation of 5-phenyl-2,3,4,5-tetrahydro-1H-benzo[b]azepine (4a), which is equivalent to photo-Claisen rearrangement of 1a. Likewise, the 1,4-diphenyl-1,4-azabutanediyl biradical Ib was generated by photolysis of 1,2-diphenylazacyclobutane (azetidine 1b). This species underwent predominating C2-C3 cleavage, as indicated by the extensive styrene formation. Although N1-C4 bond reformation also took place, this is not the major pathway occurring from Ib. Besides, C4-aryl coupling to give 4-phenyl-1,2,3,4-tetrahydroquinoline (4b) was also observed. All the possible reaction pathways were theoretically studied at the UB3LYP/6-31G computational level; the results were found to be in good agreement with the experimental observations.     

Chemistry and polymerization of 1, 1, 3, 3-tetramethyl-1, 3-disila-2-oxaindane

Reaction of o-dichlorobenzene with dimethylmethoxychlorosilane and sodium leads to the isolation of dimethyl(o-chlorophenyl) methoxysilane, o-bis(bimethylmethoxysilyl)benzene, 1,1,3,3-tetramethyl-1,3-disila-2-oxaindane, and 1, 1-dimethyl-1-silarribenzocycloheptatriene. When I is polymerized with H₂SO₄, the phenyl group is observed to split off.     

Infrared absorption spectra and structure of 1, 1, 4, 4-tetrasubstituted 1, 4-disilacyclohexanes

The IR absorption spectra of 1,1,4,4-tetramethyl- and 1,1,4,4-tetraphenyl-1,4-disilacyclohexanes have been studied. The group spectral analysis of these compounds shows that the silicon atoms have barene properties. The presence at about 980 cm^–1 of one strong band (and not two) of C-C stretching vibrations in agreement with the selection rules confirms the chair form of the heterocycle.     

Studies on 1, 2, 4-Benzothiadiazine 1, 1-Dioxide IX.1 Synthesis and Pharmacological Evaluation of 1, 2, 4-Benzothiadiazine 1, 1-Dioxide Biphenyl Tetrazoles as Angiotensin II Antagonists

In the course of our investigations on the development of cardiovascular agents, 3-butyl-2-[2′-(2H-tetrazol-5-yl)bipheny]-4-yl]methyl-2H-1, 2, 4-benzothiadiazine 1, 1-dioxide ( 2 ) was considered as a potential angiotensin II antagonist on the basis of bioisosteric replacement of the quinazoline ring of compound 1 with a 1, 2, 4-benzothiadiazine 1, 1-dioxide ring system. Alkylation of 6 with 4 afforded 7 and 8 in 24% and 28% yields, respectively. An attempt to remove the trityl group of compounds 7 and 8 under acidic condition gave the ring opened products 9 and 11 in 28% and 36% yields, respectively. However, compounds 2 and 10 were obtained in 46% and 85% yields when compounds 7 and 8 were refluxed in methanol. Preliminary assays of compounds 9 and 11 against angiotensin II receptors revealed weak activity with IC₅₀ values of 3.6 μM and 5.4 μM, respectively. Compound 10 (IC₅₀ = 87 nM) exhibited stronger binding affinity than compound 2 (IC₅₀ = 750 nM).     

1, 2-, 1, 3- and 1, 4-Cyclohexanedicarboxylates of Cd and Mn with chain and layered structures

A systematic study has been carried out on the three isomeric cyclohexanedicarboxylates (CHDCs) formed by cadmium and manganese with the three isomeric dicarboxylic acids, in the presence or absence of amines. The CHDCs have been prepared under hydrothermal conditions and their structures established by X-ray crystallography. We have been able to isolate two-dimensional layered structures of 1,2-, 1,3- and 1,4-cyclohexanedicarboxylates and chain structures of 1,3- and 1,4-cyclohexanedicarboxylates. The infinite metal-oxygen-metal linkages are observed only in the case of the 1,2-dicarboxylate. In all the three isomeric cyclohexanedicarboxylates, the e,e conformation is most favored, although the 1,4-CHDCs often contain rings in both the e,e and the a,e conformations.     

3-甲基-1a-(4-甲氧基苯基)-1, 1-二氯-1, 1a, 2, 3-四氢-吖丙 啶并[1, 2-d] [1, 5]苯并硫氮杂卓的合成和晶体结构

通过2-甲基-4-(4-甲氧基苯基)-2,3-二氢-1,5-苯并硫氮杂卓与二氯卡宾的[2+1]环加成反应制备了标题化合物,用X射线单晶衍射测定了其晶体结构。分子式C~1~8H~1~7Cl~2NOS,分子量366.30,晶体属正交晶系,空间群P~b~c~a,晶胞参数:a=1.2246(3)nm,b=1.5219(4)nm,c=1.9272(9)nm,V=3.592(2)nm^3,Z=8,D~c=1.355g.cm^-^3。位于中心的1,5-硫氮杂卓环为扭曲的类船式构象,船头与苯环并合,船底与吖丙啶环并合。     

Trifluoromethylthiolation of 1, 3- and 1, 4-Cyclohexadienes

Treatment of 1, 3-cyclohexadiene with CF 3 SCl at m 80°; furnishes 15 compounds. All but the two dimerized adducts arise from the free radical catalyzed addition of CF 3 S and Cl radicals to carbon-carbon double bonds. One dimerized product arises via dimerization of the substrate itself, while the other results from the cross-coupling of the substrate with the reaction product. The same reaction with 1, 4-cyclohexadiene gives 14 compounds. The mass spectral characterization of various compounds and their probable mechanism of formation are presented in this article.     

One-pot carbanionic synthesis of P1,P2-diglycosyl, P1,P1,P2-triglycosyl, and P1,P1,P2,P2-tetraribosyl methylenediphosphonates

Novel lithiated carbanions derived from ethyl glycosyl- and diglycosyl methylphosphonates were used in a direct and convenient synthesis of P1,P2-diglycosyl, P1,P1,P2-triglycosyl, and P1,P1,P2,P2-tetraribosyl methylenediphosphonates involving a one-pot methylidenediphosphonylation of sugars.     

Investigation of 2, 1, 3-thia- and 2, 1, 3 selenadiazoles

The nitration of naphtho[1,2-d][2,1,3]thiadiazole under the conditions that are normally used for aromatic compounds gives a mixture of 6- and 9-nitronaphthothiadiazoles, which can be reduced to 6- and 9-amino derivatives, respectively. 6-Hydroxynaphthothiadiazole is obtained from 6-aminonaphthothiadiazole by the Sandmeyer reaction, while 8-hydroxynaphthothiadiazole is converted to the 8-amino derivative under the conditions of the Bucherer reaction. 4-Carboxy-5-(o-carboxyphenyl)-2,1,3-thiadiazole was obtained by the oxidation of naphtho[1,2-d][2,1,3]-thiadiazole with a potassium dichromate-dilute sulfuric acid mixture.See [1] for communication LXVI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1496–1502, November, 1972.     

1-乙酰胺基丙叉-1,1-二膦酸和1-丙酰胺基乙叉-1,1-二膦酸与碱土金属离子的螯合作用

用pH电位法研究了1-乙酰胺基丙叉-1,1-二膦酸(S-186)和1-丙酰胺基乙叉-1,1-二膦酸(S-106)与碱土金属的螯合作用(30±O.1℃).当金属离子与配体的摩尔浓度比为10∶1、1∶1和1∶2时,在水溶液中形成了MHL、ML、ML_2和M_2L等几种类型的配合物.分别测定了它们的稳定常数,其中S-186配合物稍高于S-106,说明配合物稳定性与螯合剂的碱度有平行关系.值得注意的是,这两种螯合剂与Sr~(2 )形成的双核配合物的稳定性均较其它碱土金属离子的为高.     

Thermodynamics of the Solubility of Water in 1-Hexanol, 1-Octanol, 1-Decanol, and Cyclohexanol

Summary. The solubility of water in 1-hexanol, 1-octanol, 1-decanol, and cyclohexanol was determined as a function of water activity by the isopiestic method at 298.2K. The solubility of water in the alcohol was expressed by a Setchenov type of equation and the correlation coefficients were related to the virial coefficients of the McMillan-Mayer theory of solution. From the solubility data both the activities and the osmotic coefficients of the alcohols were calculated. The Henrys law constants for the solubility of water in the alcohols are given. They depend linearly on the Gibbs energy of hydration. The excess Gibbs energy of mixing of water and alcohols is positive as a consequence of the strong intermolecular interactions of the two pure components of the mixture.     

Reaction of 1, 1-Di-p-methoxyphenyl-2, 2-dinitroethylene and 1, 1-Di-O-methoxyphenyl-2, 2-dinitroethylene with 1-Benzyl-1, 4-dihydronicotinamide： Evidence for Concerted Electron-hydrogen Atom Transfer Mechanism

1,1-Di-p-methoxyphenyl-2, 2-dinitroethylene reacts with 1-benzyl-1, 4-dihydronicotinamide (BNAH) in deaerated acetonitrile to give 1,1-di-p-methoxyphenyl-2, 2-dinitroethane,while 1,1-di-O-methoxyphenyl-2, 2-dinitroethylene fails to react with BNAH under the same conditions, which provides evidence for a concerted electron-hydrogen atom transfer mechanism.     

Electronic, vibrational, and rotational structures in the S0 1A1 and S1 1A1 states of phenanthrene

Electronic and vibrational structures in the S(0) (1)A(1) and S(1) (1)A(1) states of jet-cooled phenanthrene-h(10) and phenanthrene-d(10) were analyzed by high-resolution spectroscopy using a tunable nanosecond pulsed laser. The normal vibrational energies and molecular structures were estimated by ab initio calculations with geometry optimization in order to carry out a normal-mode analysis of observed vibronic bands. The rotational structure was analyzed by ultrahigh-resolution spectroscopy using a continuous-wave single-mode laser. It has been demonstrated that the stable geometrical structure is markedly changed upon the S(1) ← S(0) electronic excitation. Nonradiative internal conversion in the S(1) state is expected to be enhanced by this structural change. The observed fluorescence lifetime has been found to be much shorter than the calculated radiative lifetime, indicating that the fluorescence quantum yield is low. The lifetime of phenanthrene-d(10) is longer than that of phenanthrene-h(10) (normal deuterium effect). This fact is in contrast with anthracene, which is a structural isomer of phenanthrene. The lifetime at the S(1) zero-vibrational level of anthracene-d(10) is much shorter than that of anthracene-h(10) (inverse deuterium effect). In phenanthrene, the lifetime becomes monotonically shorter as the vibrational energy increases for both isotopical molecules without marked vibrational dependence. The vibrational structure of the S(0) state is considered to be homogeneous and quasi-continuous (statistical limit) in the S(1) energy region.