1, 1, 1-Trichloropropanone: A Mild,Selective Acetylating Agent

The use of the title compound in the acetylation of primary and secondary amines i s described.     

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.     

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).     

Synthese von 1, 2-annelierten 1, 4-Benzodiazepinen und 4, 1-Benzoxazepinen

The syntheses of 1, 2-annelated 1, 4-benzodiazepines (IV, Y = N) and 4, 1-benzoxazepines (IV, Y = 0) are described (Scheme 1). The key step is a nucleophilic aromatic substitution of 2-substituted piperazines (II, Z = N? CH₃), piperidines (II, Z = CH₂) or pyrrolidines (II, Z= (CH₂)₀) with activated aryl halides (I).     

Reaction of 1, 1-dichloro-1-nitrosobutane with N,N-dimethylamidodichlorophosphite

Conclusions 1,1-Dichloro-1-nitrosobutane reacts exothermally with N, N-dimethylamidodichlorophosphite to give N,N-dimethylamidotetrachlorophosphorane and a nitrile oxide. In the presence of SO₂,this reaction gives O-propylchloroformimino-N, N-dimethylamidochlorophosphate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1416–1418, June, 1989.     

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。     

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.     

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.     

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.     

Raman- und Infrarotspektren isotaktischer Poly-α-olefine III: Polydodecen-1, Polytetradecen-1, Polyhexadecen-1, Polyoctadecen-1

Zusammenfassung DieRaman- und Infrarotspektren der isotaktischen Poly--olefine Polydodecen-1, Polytetradecen-1, Polyhexadecen-1 und Polyoctadecen-1 wurden bei verschiedenen Temperaturen gemessen, um den Einfluß der Seitenketten auf den Ordnungszustand innerhalb dieser Polymeren zu untersuchen. Aus den Spektren der langsam aus der Schmelze abgekühlten Proben kann geschlossen werden, daß sich die meisten Methylengruppen der Seitenketten in einer planaren TT-Konformation befinden. Mit Beginn des ersten endothermen Peaks der DTA-Kurve wird eine Änderung dieser Struktur beobachtet. Die gegenüber dieser Änderung des Ordnungszustandes besonders empfindlichen Banden finden sich in denRamanspektren im Bereich der CH₂-bending-Schwingungen und im Bereich der CH₂-rocking-Schwingungen bei den Infrarotspektren.

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Summary For studying the influence of the side-chains on the state of orderRaman and infrared spectra of the isotactic poly--olefins polydodecene-1, polytetradecene-1, polyhexadecene-1 and polyoctadecene-1 were measured at different temperatures. The spectra of the slowly cooled samples show that most sidechain methylene groups form a planar TT-conformation. A change in this structure is observed at the beginning of the first endothermic DTA peak. The most sensitive bands due to this change in the state of order can be found in theRaman spectra in the range of the CH₂-bending vibration and in the infrared spectra in the range of the CH₂-rocking vibration.

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Mit 9 Abbildungen und 2 Tabellen     

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.     

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.     

Triterpene glycosides ofHedera canariensis. I. Structures of glycosides L-A,L-B1, L-B2, L-C,L-D,L-E1 1, L-G1, L-G2, L-G3, L-G4, L-H1, L-H2, AND L-I1 from the leaves ofHedera canariensis

From the leaves of Algerian ivyHedera canariensis Willd. (fam. Aralaceae) we have isolated 13 triterpene glycosides: the 3-O--L-arabinopyranosides of oleanolic acid (A), of echinocystic acid (B₁), and of hederagenin (B₂); the 3-O-[O--L-rhamnopyranosyl-(2)--L-arabinopyranoside]s of oleanolic acid (C), of echinocystic acid (D), and of hederagenin (E₁); the 3-O--L-rhamnopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--gentiobioside of hederagenin (G₁); the 3-O-[O--L-rhamnopyranosyl-(12)--L-arabinopyranoside] 28-O--gentiobioside of hederagenin (G3); the 3-O-[O--L-rhamnopyranosyl-(12)--L-arabinopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--gentiobioside]s of oleanolic acid (G₂), of echinocystic acid (H₁), and of hederagenin (H₂); the 3-O-[O--L-rhanmopyranosyl-(12)--D-glucopyranoside] 28-O-(O--L-rhamno-pyranosyl-(14)--gentiobioside] of hederagenin (H₂); and the 3-O-(O--L-rhamnopyranosyl-(12)-O-gentiobiosyl)-O-(14)--L-rhamnopyranosyl-(12)-a-L-arabinopyranoside] of hederagenin (G₄). The structures of the substances isolated have been established on the basis of chemical transformations and¹³C NMR spectroscopy.Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 377–383, May–June, 1996. Original article submitted December 3, 1995.     

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.