Synthesis ofS-(+)-hydroprene

A novel path toS-(+)-hydroprene (1) starting from the technical gradeS-(+)-dihydromyrcene (2, e.e. 50%) is proposed. The latter was selectively transformed intoS-3,7-dimethyloctanal (5) in three steps including hydroalumination. The reactions of5 with allyl- or methallylmagnesium chloride followed, respectively, either by oxygenation in the presence of PdCl₂/CuCl or by ozonolysis, affordS,E-6,10-dimethyl-3-undecen-2-one (7) which was treated with ethoxyethynylmagnesium bromide to give the title juvenile hormone analogue in 23% overall yield.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 1, pp. 110–112, January, 1993.     

Correlation of the position of the bond functions in H-X with electronegativity

S type Gaussian bond functions are optimized for HF, H₂O, NH₃, and CH₄. The optimization is carried out with respect to the exponent and position in the H-X bond. The position is found to correlate well with the electronegativity of Pauling and Allred-Rochow.     

钌（Ⅱ）－联吡啶－巴比妥酸－Ce（Ⅳ）化学发光体系测定巴比妥酸的研究

利用巴比妥酸对Ｃｅ（Ⅳ）氧化钌（Ⅱ）－联吡啶化学发光反应的增强作用，建立了痕量巴比妥酸的自动脉冲注射化学发光测定法方法的检出限为１０×１０－９ｇ／ｍＬ，线性范围为５０×１０－８－６．２×１０－５ｇ／ｍＬ巴比妥酸的衍生物如巴比妥、苯巴比妥和戊巴比妥对Ｃｅ（Ⅳ）氧化钌（Ⅱ）联吡啶化学发光反应无增强作用据此对合成样中巴比妥酸作选择性检测探讨了巴比妥酸的增强机理     

Captodative olefins: methyl 2-aryloxy-3-dimethyl-aminopropenoates and their application in a new synthesis of benzofurans

The β-substituted captodative olefins methyl 2-aryloxy-3-dimethylaminopropenoates 4a-h were synthesized, via aminomethylenation of the corresponding 2-phenoxyacetic esters 9a-h. Lewis acid promoted intramolecular cyclization of alkenes 4 led to benzofurans 7a-h, in an efficient synthetic approach to the benzofuran frame.     

Theoretical investigation of 1,4-dioxane complexes with water in the <Emphasis Type="Italic">chair</Emphasis> conformation by semiempiric MNDO/PM3 method

The structure and relative stability of 1,4-dioxane-water, (Diox)_n·(H₂O )_m (n = 1, 2, m = 1–6), molecular complexes have been calculated by semiempirical MNDO/PM3 method. A considerable variety of (Diox)_n·(H₂O )_m isomeric structures was stated. The mean energy of O_Diox…H_W-O_W hydrogen bond in (Diox)_n·(H₂O)_m complexes formed by 1,4-dioxane molecules in the chair conformation amounts to ?2.293 ± 0.210 kcal/mol with the average bond length 2.797 0.015 Å.     

Recent Applications of α-Metalated Isocyanides in Organic Synthesis

Being both nucleophilic and electrophilic, α-metalated isocyanides can add to polar double bonds, forming heterocycles. They are also synthons for α-metalated primary amines. This article describes recent or improved procedures for their use in organic synthesis: (1) In heterocyclic syntheses to give 2-oxazolines, 2-imidazolines, 2-thiazolines, oxazoles and oligooxazoles, thiazoles, triazoles, imidazolinones, pyrroles, 5,6-dihydro-1,3-oxazines and -thiazines, and (via cycloaddition with nitrones) 2-imidazolidinones. (2) In the field of formylaminomethylenation, for example transformation of estrone methyl ether and a keto sugar into the corresponding α-formylaminoacrylic esters, and the conversion of aldehydes and ketones by 3- and 4-pyridyl-methyl isocyanides into N-(1-pyridyl-1-alkenyl)formamides and their hydrolysis to 3- and 4-acylpyridines. (3) In connection with the use of α-metalated isocyanides as synthons for α-metalated primary amines, the author demonstrates how they may be used for preparation of 1,2- and 1,3-amino alcohols, 1,2-diamines, 2,3-diaminoalkanoic acids and for synthesis of higher amino acids starting from simple amino acids.     

Rearrangement during cyclisation of some 3-(2-pyrrolyl) propionic acids and related compounds

Cyclisation of the title compounds leads to mixtures of the expected 4H-cyclopental[b]pyrrol-4-ones (1), the corresponding 6-ones (3) by a single rearrangement, and the cyclopenta[c]pyrrol-4-ones (4) by a double rearrangement, the proportions depending upon the substituents.The ¹H NMR spectra of 2-methyl-4H-cyctopenta[b]thiophen-6-one (3f) shows 6J long range $\text{CH}{}_3\text{CH}{}_2$ coupling, but this is absent in the corresponding pyrroles (3c,d). The ¹³C spectra of 1 and 3 cannot be interpreted on the basis of substituent chemical shifts in pyrroles and thiophens, and are clearly -CH = CH-X (X = NMe, NPh, S) bridged derivatives of cyclopent-2-enone.     

Complexation of Ni (II) and Zn(II) ions by 3-(1-naphthyI)-2-mercaptopropenoic acid

The complexation equilibria between Ni(II) and Zn(II) metal ions with 3-(1-naphthyl)-2-mercaptopropenoic acid (H₂NMP) were studied by glass electrode potentiometry, at 25 °C and 1.0 mol·dm^–3 in NaClO₄ as constant ionic medium in 50% (v/v) water-ethanol solutions. Formation constants for the complexes Ni(NMP), Ni(NMP) ₂ ^2– , Zn(NMP) and Zn(NMP) ₂ ^2– , refined by the MINIGLASS program, are reported.     

计算旋转螺旋面三维边界层的一种积分方法

本文将计算二维层流边界层的Thwaites方法和计算二维湍流边界层的Truckenbrodt方法推广,用以求解旋转系统的“准三维”边界层方程,得到了计算旋转螺旋面上三维边界层的一种可迭代求解的积分方法.应用此方法进行了两例计算.计算结果与理论精确解或实验测量的对比表明,本文方法是有效的.     

WS~*-闭空间的性质

该文引入了一类包含Ｓ－闭空间的拓扑空间——ＷＳ＊－闭空间,并讨论了它的一些性质,对一些关于Ｓ－闭空间的已知命题,建立或推广得到ＷＳ＊－闭空间的相应命题。