Reactions of protoberberine-type alkaloids—XI : Synthesis of optically active ochotensanes

Treatment of l(14S)-β-canadine methochloride (1b) and d(14R)-β-canadine methochloride (1c) with organometals gave d- (2b) and l-2,3-methylenedioxy-9,10-dimethoxyochotensanes (2c), respectively. The structures of these derivatives were proved by chemical and spectral means. The CD spectra of 2b showed Davydov split extrema centered at 284 nm with a positive first Cotton effect, while 2c showed the antipodal curve of 2b. Consequently, the absolute configurations of 2b and 2c were concluded the 14R and 14S, respectively.Application of the anionic rearrangement to N-methyltharictricavine chloride (15) led to 2,3 - methylenedioxy - 9,10 - dimethoxy - 13 - methylochotensane (18) together with the Hofmann methines 16 and 17. The stereochemistry of 18 was confirmed in terms of the nuclear Overhauser effects.     

Gas chromatographic determination of estrone,estradiol and estriol in non-pregnancy plasma

Summary A gas Chromatographic method for the determination of estrone, estradiol and estriol in plasma of normal females is described. Purification is done by means of TLC of the free compounds and the acetates and quantitation is achieved by electron capture-gas chromatography of the estrogen heptafluorobutyrates. Experiments on the validation of the method are described along with some examples of its application.

---

Zusammenfassung Eine gaschromatographische Methode zur Bestimmung von Östron, Östradiol und Östriol im normalen weiblichen Plasma wurde beschrieben. Die Reinigung erfolgte durch Dünnschichtchromatographie der freien Verbindungen und ihrer Acetate. Die quantitative Bestimmung wurde gaschromatographisch mit Hilfe eines Elektroneneinfangdetektors an Hand der Östrogenheptafluorobutyrate bewerkstelligt. Versuche zur Bewertung dieser Methode sowie Beispiele für ihre Anwendung wurden beschrieben.

---

---

Supported by USPHS Grants AM 09908 and RCDA 5 K 3-AM-31, 321 (S. K.) and a grant from the Ford Foundation.     

Sequential transition States and the valley-ridge inflection point in the formation of a semibullvalene

[structure: see text] Two sequential transition states are calculated at the B3LYP/6-31G(d,p) level for the deazetization of 3b. The intrinsic reaction coordinate for loss of nitrogen passes through a transition state and then a valley-ridge inflection point and ultimately leads to the transition state for the Cope rearrangement of semibullvalene 4b. The energetic and geometrical consequences are discussed.     

Studies on the synthesis of condensed pyridazine derivatives. IV. Synthesis and anxiolytic activity of 2-aryl-5,6-dihydro-(1)benzothiepino[5,4- c]pyridazin-3(2H)-ones and related compound.

A series of 2-aryl-5,6-dihydro-(1)benzothiepino[5,4-c]pyridazin-3(2H)- ones and related compounds were synthesized and evaluated for their ability to displace 3H-diazepam from rat brain membranes in vitro, and to prevent bicuculline induced convulsions in mice in vivo. Compounds with a 4'-methoxyphenyl (36) or 4'-chlorophenyl group (37, 39--42) as 2-aryl substituents showed prominent activities in both the in vitro and in vivo tests. Among them, 2-(4'-chlorophenyl)-5,6-dihydro- (37) and 2-(4'-chlorophenyl)-5,6-dihydro-10-fluoro-(1)benzothiepino[5,4-c]+ ++pyridazin- 3(2H)-one 7-oxides (41) showed activity twice as potent as diazepam in an anticonflict test (Vogel type, rats) while exhibiting less muscle relaxation (rotarod test, mice) and augmentation of gamma-aminobutyric acid-induced chloride current (Icl) in isolated frog sensory neurones than diazepam. Compound 37 (Y-23684) was selected from this series as a candidate for further development. The structure-activity relationships are discussed.     

气液色谱法研究一些五员杂环和Ni[CF_3COCHC(C_4H_4S)=NCH_2]_2加合反应的热力学性质

用气液色谱法研究过一系列作为Lewis碱(B)的有机配体和作为Lewis酸(A)的配合物之间的加合作用.研究较多的碱已有脂肪醇、醚、酮、醛、脂及胶等.对生物体系中广为存在的杂环配体碱的工作还很少.本文着重研究噻吩,呋喃和吡咯这类小分子杂环配体和Ni[CF_3COCHC(C_4H_4S)=NCH_2]_2(以下简称A)配合物的加合反应. Ni[CF_3COCHC(C_4H_4S)=NCH_2]_2的合成参考文献.固定液角鲨烷系英国进口,     

A new pharmacological testing method--different effects of levamisole and the serum of mice orally treated with levamisole on mitogenic activity of lipopolysaccharide

The direct addition of levamisole to murine splenic lymphocytes had no effect on the mitogenic activity of lipopolysaccharide. However, the addition of serum of mice orally treated with levamisole increased the mitogenic activity, and this increased activity using serum was similar to the result obtained in an in vivo experiment. These results suggest that the new in vitro experimental method using serum may be able to reproduce the in vivo effect of drugs.     

Infrared study of co adsorbed species on ru/silicalite catalyst

Carbon monoxide adsorbed species on Ru/silicalite and their reactivity towards oxygen have been studied using in situ diffuse reflectance infrared spectroscopy (DRIFT). Four species were detected: a bridge bonded CO on metallic Ru (1980 cm ^-1), a linearly adsorbed CO on metallic Ru (2040 cm^-1), a linearly adsorbed CO on partially oxidized Ru (2081 cm^-1), and a multicarbonyl on oxidized Ru (2081 and 2133 cm^-1). Among the four CO species the most strongly held species was the bridge bonded CO on metallic Ru while the multicarbonyl was the most weakly held species. These four species have different reactivities towards oxygen. Only the linearly adsorbed CO on metallic Ru can be oxidized at room temperature.     

RP-HPLC测定兔血清和脑脊液中甲硝唑含量

 报告了用RP-HPLC测定免血清和脑脊液中甲硝唑浓度的方法，采用ZorbaxC8柱，NaH2PO4水溶液（0.0075mol／L）-甲醇（4:1，PH4.0）为流动相，氢氯噻嗪为内标，检测波长320um。线性范围0.5～80mg／L，最低检出浓度80μg／L（信噪比为3）。     

三(2-苯并咪唑亚甲基)胺硝酸镍(Ⅱ)配合物的合成及结构

三（２－苯并咪唑亚甲基）胺简称ＮＴＢ与Ｎｉ（Ⅱ）的硝酸盐形成配合物Ｃ２８Ｈ３５Ｎ９Ｏ９Ｓ２Ｎｉ。本文报道其合成，红外光谱及晶体结构。该化合物为三斜晶系，空间Ｐ１↑－，ａ＝９．６５０（３），ｂ＝１２．７１６（２），ｃ＝１４．４３６Ａ，α＝１１．４６（２），β＝９１．６６（３），γ＝９７．５５（２）°，Ｖ＝１７１８（２）Ａ＾３，Ｚ＝２，Ｆ（０００）＝７９３，Ｄｃ＝１．４８ｇ／ｃｍ＾３，Ｍｒ＝７６４．１