Studies in oxasteroids—I : Synthesis of 3-cyano-3-methyl-7-methoxychroman-4-one and the structure of an “abnormal” product

A synthesis of 3-cyano-3-methyl-7-methoxychroman-4-one is reported. The structure of an “abnormal” product obtained during isomerization (III) with potassium t-butoxide in t-butanol, followed by alkylation with methyl iodide has been proved to be 3-t-butoxy-2-cyano- 2-mehthyl-2′,4′-dimethoxypropiophenone (IVa).

A revised structure for the condensation product of 2-carbethoxycyclopentanone and ethyl cyanoacetate

The condensation product of 2-carbethoxycyclopentanone and ethyl cyanoacetate is ethyl 2-carbethoxycyclopentylidene cyanoacetate (IIa) and not the one described by Kon and Nanji. Similarly, 2-carbomethoxycyclopentanone and methyl cyanoacetate yield methyl 2-carbomethoxycyclopentylidene cyanoacetate (IIb). The by-products obtained in the first reaction are cyclopentylidene cyanoacetate (IV) and the enamine of 2-carbethoxycyclopentanone (VIa).

Bufadienolides. 8. 12(13→14)abeo skeletal rearrangements

Several methods were developed for converting isodigitoxigenin (2a) into methyl acetals 4b and 4c. Of these, methanolysis (followed by acetylation) of isodigitoxigenin in the presence of p-toluenesulfonic acid proved most useful. Each isomer reached an equilibrium corresponding to ca. 3:1 acetal 4c to 4b within 15 min in benzene containing p-toluenesulfonic acid. Addition of dihydropyran to the equilibrium mixture resulted in excellent conversion into vinyl ether 5a. Heating either acetal 4b or 4c in benzene containing p-toluenesulfonic acid led to a skeletal rearrangement culminating in formation of C-norcardenolide 6. In addition to results of physical measurements, the structure of spiran 6 was confirmed by degradation to methyl ketone 8. Similar rearrangement of isodigitoxigenin gave spiran 9 accompanied by C-norcardenolide 6. Treating lactone 9 with p-toluenesulfonic acid in methanol-water provided acetals 10a and 10b, which on further contact with p-toluenesulfonic acid in refluxing benzene gave lactone 9 and cardenolide 6. Evidence underlying the stereochemical assignments noted for structures 4, 9, and 10 was also discussed.

Structure of abnormal products isolated from the isomerization of 7-methoxychromano3,4-disoxazole - A novel synthesis of one of the products

A one-step synthesis of (IIb), an isomerization product of 7-methoxychromano3,4-disoxazole, from (III) is reported.

The structure of thiostrepton

Much of the chemical structure of thiostrepton, a sulphur containing metabolic product of the microorganism Streptomyces azureus, has been determined by X-ray crystallographic techniques.

Reactions of tetrahalogeno-1,2-benzoquinones. Part III. Reaction of tetrachloro-1,2-benzoquinone with tetralones and naphthols: Pathway to the condensates

With a view to understanding the mechanism of the formation of 6-methoxy-2,2-(tetrachloro--phenylenedioxy)-naphthalen-1 (2H)-one (IIIa) in the reaction of 6-methoxy-1-tetralone (Ia) with tetrachloro-1,2-benzoquinone (II), the reaction of (II) with various tetralones and naphthols has been studied. Reaction with either α-tetralone or α-naphthol gives 2,2-(tetrachloro-o-phenylenedioxy)naphthalen-1 (2H)-one (IIIb), whereas reaction with either β-tetralone or β-naphthol gives a mixture of (IIIb) and ,1-(tetrachloro-o-phenylenedioxy)-naphthalen-2 (1H)-one (IX), with the former predominating. Further, reactions of (II) with 7-methoxy-3,4-dihydrophenanthren- 1 (2H)-one and m-methoxyphenol gave respectively 7-methoxy- ,2-(tetrachloro-o- phenylenedioxy)phenanthren-1 (2H)-one (VII) and 3-methoxy-6,6-(tetrachloro-o- phenylenedioxy)cyclohexa-2,4-dien-1-one (VIII). Structures of all these compounds have been proved on the basis of i.r. and n.m.r. data. The pathway to the formation of the condensates (III) is discussed.

Assessment of Nanoscience and Nanotechnology Initiatives in India

Nanotechnology is a new technology which is generating a lot of interest among academicians, practitioners and scientists. Critical research is being carried out in this area all over the world.Governments are creating policy initiatives to promote developments it the nanoscale science and technology developments. Private investment is also seeing a rising trend. Large number of academic institutions and national laboratories has set up research centers that are workingon the multiple applications of nanotechnology. Wide ranges of applications are claimed for nanotechnology. This consists of materials, chemicals, textiles, semiconductors, to wonder drug delivery systems and diagnostics. Nanotechnology is considered to be a next big wave of technology after information technology and biotechnology. In fact, nanotechnology holds the promise of advances that exceed those achieved in recent decades in computers and biotechnology. Much interest in nanotechnology also could be because of the fact that enormous monetary benefits are expected from nanotechnology based products. According to NSF, revenues from nanotechnology could touch $ 1 trillion by 2015. However much of the benefits are projected ones. Realizing claimed benefits require successful development of nanoscience andv nanotechnology research efforts. That is the journey of invention to innovation has to be completed. For this to happen the technology has to flow from laboratory to market. Nanoscience and nanotechnology research efforts have to come out in the form of new products, new processes, and new platforms.India has also started its Nanoscience and Nanotechnology development program in under its 10(th) Five Year Plan and funds worth Rs. One billion have been allocated for Nanoscience and Nanotechnology Research and Development. The aim of the paper is to assess Nanoscience and Nanotechnology initiatives in India. We propose a conceptual model derived from theresource based view of the innovation. We have developed a structured questionnaire to measure the constructs in the conceptual model. Responses have been collected from 115 scientists and engineers working in the field of Nanoscience and Nanotechnology. The responses have been analyzed further by using Principal Component Analysis, Cluster Analysis and Regression Analysis.

A preliminary survey of dermatomycoses in Bangalore

Clinical and mycological investigations were made on 225 cases of suspected dermatomycoses. Of these, 102 were microscopically positive. But only 63 were culturally positive, and these are analysed here with regard to clinical patterns and aetiological species, age, sex and occupational incidence and susceptibility to griseofulvin in vitro. As in most other parts of India, Trichophyton rubrum was the dominant species. A high proportion of Epidermophyton floccosum was an unusual feature seen. Of the clinical types, tinea cruris was the most common. The isolates were sensitive to griseofulvin at low concentrations of 1 to 5 μg per ml of agar medium, E. floccosum being the most sensitive.

Kuviteltu aatelismies : Aateluus viholliskuvana ja itseymmärryksenä 1800-luvun Suomessa

An imagined nobleman Nobility as an enemy image and in-group identity in nineteenth-century Finland The focal point of this study is the difficult relationship between two seemingly very different 19th-century elite groups, the upwardly mobile bourgeois intelligentsia and the slowly declining traditional nobility. In the thinking of the bourgeois contender the two emerged as exact opposites, styled as conflicting ideal types: an outdated, exclusive, degenerate hereditary aristocracy versus a dynamic and progressive new force in society, recruited solely on the basis of personal merit, originating from the common people and representing the nation. The appearance of an important 19th-century novelty, print publicity, coincided with the emergence of the bourgeois intelligentsia. The institutions of the developing publishing industry were manned by the aspiring new group. The strengthening flow of progressive, democratic, nationalist ideas distributed via the printing presses carried an undercurrent of self-promotion. It transmitted to the developing readership the self-image of the new cultural bourgeoisie as the defender and benevolent educator of the nation. Having won the contest over the media, the intelligentsia was free to present its predecessor and rival as an enemy of the people. In its politics the nobility emerged as an ideal scapegoat, represented as the source for existing social evils, all if which would promptly go away after its disappearance. It also served as a black backcloth, against which the democratic, national, progressive bourgeois intelligentsia would shine more brightly. In order to shed light on the 19th-century process of (re)modelling the image of nobility as a public enemy I have used four different types of source materials. These include three genres of print publicity, ranging from popular historical and contemporary fiction to nonfictional presentations of national history and the news and political commentaries of the daily papers, complemented by another, originally oral type of publicity, the discussion protocols of the Finnish four-estate parliament. To counterpoint these I also analysed the public self-image of the nobility, particularly vis-à-vis the nationalist and democratic ethos of the modernising politics.

Electron-metallographic studies of precipitation in an aluminium-zinc-magnesium alloy

The mechanism of sub-microscopic precipitation in an Al-Zn-Mg alloy selected for its maximum response to ageing has been studied by a standardized oxide-replica technique in a 100 kV. Philips Electron Microscope. Contrary to earlier conclusions, examination of the oxide replicas has been shown to reveal details of the precipitation process almost as clearly as the thin-foil transmission technique. The reported formation of spherical Guinier-Preston zones followed by the development of a Widmanstaetten pattern of precipitated platelets has been confirmed. The zones have, however, been shown to grow into the platelets and not to dissolve in the matrix as reported earlier. The precipitation process has been correlated with the Hardness/Ageing Time curve and the structure of the precipitates has also been discussed.

Steroids and related natural products. VIII. Synthesis of oxasteroids

Peroxydisulfuric acid oxidation of testosterone propionate, progesterone, and cholest-4-en-3-one has been shown to yield 3-oxo-17β-hydroxy-4-oxa-5α-androstane (I, after saponification), 3,20-dioxo-4-oxa-5α-pregnane (V) and 3-oxo-4-oxa-5α-cholestane (VII) respectively. Boron trifluoride etherate-lithium aluminum hydride reduction of δ-lactones I, V, and VII led to the corresponding tetrahydropyran derivatives (IIb, VIa, and VIII). Similar reduction of 3β-hydroxy-17-oxo-17a-oxa-D-homo-5α-androstane (XI) gave 3β-hydroxy-17a-oxa-D-homo-5α-androstane (XIIa). Diborane-boron trifluoride etherate was also found to reduce lactones to cyclic ethers, while reduction with diborane gave hemiacetals. Evidence in support of the structures and stereochemistry assigned to the lactones and their unusual reduction products has been summarized. A tentative mechanism is proposed for lactone → ether reduction employing diborane-boron trifluoride etherate.

Steroids and related natural products. VII. Boron trifluoride etherate-lithium aluminum hydride reduction of smilagenin acetate

Reduction of smilagenin acetate (Va) using a boron trifluoride etherate-lithium aluminum hydride reagent, followed by hydrogen peroxide oxidation and acetylation, was found to yield: 3β-ethoxysmilagenin (Vb), 3β-ethoxydihydrosmilagenin acetate (VIa), dihydrosmilagenin diacetate (VIb), and a complex mixture of partially acetylated products. Similar reaction conditions were employed to convert dihydrodiosgenin (II) to dihydrochlorogenin (III). Boron trifluoride etherate-lithium aluminum hydride reduction of 3β-acetoxy-5α-cholestane and 3β-acetoxy-5α-lanostane (VIIIa) was shown to yield the corresponding 3β-ethoxy (e.g., VIIIb) derivatives.

Dipole moments and molecular structure of picrates of aromatic hydrocarbons and heterocyclic amines

Dipole moment measurements have been made in the case of a few aromatic hydrocarbon picrates, the values obtained being 2·18, 2·25, 2·97 (all in Debye units) for picrates of naphthalene, acenaphthene and phenanthrene respectively and the results discussed in terms of Mulliken's theory. Measurements have also been extended to include a few salt-like heterocyclic amine picrates.