THERMAL AND PHOTOCHEMICAL REACTIONS BETWEEN α, α′-DIBROMOKETONES AND FIVE-MEMBERED HETEROCYCLES IN THE PRESENCE OF IRON NONACARBONYL

Abstract

[3 + 4] Cycloaddition reactions of 2-oxyallilic cations to furan¹ to form seven-membered oxobicyclic compounds have been known for some time. The purpose of this paper has been to try to extend the reaction to five-membered heterocycles with more aromatic character than furan. An analogy has been found between the behavior of thiophene, selenophene and tellurophene in these reactions and in oxetane-forming reactions. The higher the aromaticity of the heterocycle, the more difficult it is to achieve the formation of the seven-membered ring. Contrary to what is observed in oxetane-forming reactions, where it is not possible to isolate a stable tellurium compound, the tellurabicyclic compound was isolated and identified by spectroscopic methods in the present investigation.     

SYNTHESIS AND REACTIVITY OF ENDOCYCLIC α-CYANOENAMINES IN THE PHENYLOXAZOLOPIPERIDINE SERIES

Using the capto-dative character of piperidine building block 1, the diastereomeric α-cyanoenamines 2a and 2b accompanied by dimer 5 were prepared through a SET pathway in a one-step procedure. Adjustment of the reaction conditions afforded either 2a or 2b as the major constituent. γ-Alky- lation of 2b with benzyl bromide proceeded smoothly.     

MHEORETICAL STUDIES ON THE REACTION MECHANISMS OF CYCLOADDITION REACTIONS BETWEEN KETENE OR SUBSTITUTED KETENES AND CYCLOPENTADIENE

The cycloaddition reactions between ketene or substituted ketenes andcyelopentadiene have been studied theoretically by means of the semiempirical AMImethod.Three different substituted ketenes have been selected and tentransition states,corresponding to different approach geometries have beenlocated and characterized,The regioselectivity and stereoselectivity of thereactions are correctly predicted by the calculations and the reaction mechanismsare analyzed in terms of electronic and steric effects of the substitutents onthe reacting ketene and cyc-lopentadiene.     

DEHYDROCHLORINATION OF α-CHLORO SULFONES WITH KOH-T-BUOH: KINETIC VS EQUILIBRIUM CONTROL OF THE FORMATION OF α, β-UNSATURATED SULFONES AND THE β-T-BUTOXY AND β-HYDROXY MICHAEL ADDUCTS

Abstract

Inorganic sulfur compounds are used by microorganisms (bacteria, fungi, algae) and plants for assimilation, i.e. biosynthesis of sulfur-containing cell constituents.

Quantitatively, within the biogeochemical cycle of sulfur the utilization of inorganic sulfur compounds in bacterial energy metabolism, i.e. dissimilatory sulfur utilization, is of far higher importance. Reduced sulfur compounds serve as electron donors for photosynthesis and respiration, whereas inorganic sulfur compounds of oxidation levels above sulfide serve as electron donors in anaerobic respiration as well as in fermentation. In still other bacteria reduced sulfur compounds act as protective agents against hydrogen peroxide.     

CORE BINDING ENERGIES OF SOME METAL β-DIKETONATES AND β-DIKETONES IN THE VAPOR PHASE

Abstract

The vapor-phase core binding energies of some tris β-diketonates of A1(III), V(III), Cr(III), and Fe(III) and of two β-diketones have been measured. The rather large shifts observed for the A1 2p energies are believed to be caused mainly by changes in the electrostatic potential at the A1 atom due to changes in the charges of the ligand atoms. Considerable resonance relaxation energy is associated with the core ionization of the carbonyl carbon atoms and the CH carbon atoms. The data for the metal hexafluoroacetylacetonates show that the metal d orbitals are not significantly involved in the bonding and suggest that there is no strong ligand → metal donor bonding.     

THE SYNTHESES OF POLYQUINOLINES WITH 2,2''''-PYRIDYLQUINOLINE AND 2,6-DIQUINOLYLPYRIDINE AS LIGAND AND THEIR APPLICATIONS IN SOME CATALYTIC REACTIONS

The polyquinolines with 2,2'-pyridylquinoline as bidentate and 2,6-diquinolylpyridine as tridentate ligand have been prepared from 4,4-dlamino- 3,3'-dibenzoyldiphenyl ether, 4,4'-diacetyldiphenyl ether and 1,4-bis (2-acetylpyridyl-6-oxy) benzene, 2,6-diacetylpyridine, respectively. These polyquinoline-supported ligands have been used in hydrogenation and hydroformylation of olefins with some transition metal complexes.     

REACTIONS BETWEEN BORIC ACID AND POLYHYDROXY COMPOUNDS AND THE DEVELOPMENTS OF BORON—SELECTIVE RESINS

A Review with 56 references on the reaction between boric acid and polyhydroxy compounds,and the developments of boron-selective resins.     

REACTIONS BETWEEN BORIC ACID AND POLYHYDROXY COMPOUNDS AND THE DEVELOPMENTS OF BORON－SELECTIVE RESINS

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STUDIES ON THE RELATIONSHIP BETWEEN THE TR SPECTRA AND THE STRUCTURE OF SOME LINEAR Mo-Fe-S CLUSTERS

<正> The IR spectra of seven linear Mo-Fe-S clusters have been investigated. The characteristic frequencies VMo-st, VMo-sb, VFe-sb, VFe-spb and VFe-cl were assigned by comparing their vibratiional frequencies with the structural parameters and oxidation states of the metals in these clusters. The assignment of δS-Mo-S was attempted to approach. The influence ofMo atom on Vre-sb in the clusters containing heteronuclear MoS2Fe unit hasbeen discussed. The internal relationship and regularity between the characteristic frequencies and some structural parameters were demonstrated. Final a valuable parameter ΔV, which may be taken as a qualitative estimate of the extent of .Fe →Mo charge transfer in Mo-Fe-S clusters, was proposed.     

STUDY OF THE REACTION BETWEEN α-KETOTHIOANILIDE AND PHENYLENE DIAMINE

When α-ketothioanilide reacts with o-phenylenediamine,there aretwo competing reactions.One is condensation which forms substituted quinoxalineand the other is substitution which forms substituted quinoxaline-2-thione·Bycontrolling the reaction condition,we can obtain either quinoxaline orquinoxaline-2-thione as the main product.     

FACTORS IN THE CONTROL OF PRODUCT COMPOSITION IN THE REACTIONS OF TRIALKYL PHOSPHITES WITH α-HALOGENOACETOPHENONES IN ALCOHOLIC MEDIA

Abstract

α-Hydroxyphosphonates are formed, in addition to vinyl phosphates and dehalogenated ketones, in the reactions of trimethyl phosphite (in methanol) or triethyl phosphite (in ethanol) with variously substituted α-chloro, α-bromo, and α,α-dichloro-acetophenones. Tri-isopropyl phosphite in propan-2-ol gives only the vinyl phosphate. Ketophosphonates are not detectable amongst the reaction products under the conditions used. Trends in product composition can be correlated with the leaving ability of halogen, substituent effects, structure of the phosphite, and reaction temperature. Additional products are obtained in the reactions of trimethyl phosphite in methanol with 4-nitro-α-chloroacetophenone, which gives the dehalogenated hydroxyphosphonate, and with the α,α-dichloroacetophenones which undergo monodehalogenation. Twenty three new α-hydroxyphosphonates are reported.     

CORRELATION BETWEEN δD AND H_2O IN SOME GRANITOID OF CHINA

The correlation between δD and H_2O content in granitoid can be divided into threetypes: closed-system crystallization type (Darongshan type): a flat positive linear corre-lation; open-system degassing type (Laoshan type): a nearly vertical linear positive cor-relation; meteoric hydrothermal exchange type (Gabug type): an irregular negative trendcorrelation.     

CATALYTIC SYNTHESIS OF α-CYANO-α,β-UNSATURATED SULPHONES IN THE PRESENCE OF ORGANOTELLURIUM OXIDE

Using bis(p-methoxyphenyl)telluroxide(BMPTO)as the catalyst,phenylsulphonyl acetonitrile condensed easily with aromatic aldehydes atroom temperature to give -cyano- ,β-unsaturated sulphones in high yields.     

CONCENTRATION, SOURCE OF MANGANESE AND IRON IN FERROMANGANESE NODULES AND THE RELATIONSHIP BETWEEN NODULES AND SEDIMENTARY ENVIRONMENTS IN NORTH PACIFIC REGION

The concentration, source of manganese and iron in ferromanganese nodules and therelation between nodules and sedimentary environments are discussed in detail by asynthetical study on chemical information of ferromanganese nodules and correspondingsediment, pore water and geological, biological (bacteria) information in 26 stations fromthe North Pacific region (7- 13°N, 178- 165°W). The result shows that (i) the concen-tration and distribution characteristics of magnese and iron in ferromanganese nod-ules differ in different types of nodules, however, the concentration decreases with theincrease in grain sizes of nodules; (ii) the source of iron in different types of nodulesis basically the same, i. e. the slow sedimentation of overlying water; (iii) manganesein nodules comes mainly from the diffusion of Mn~(2+) in the pore water, and Mn~(2+) fromthe reduction of Mn~(4+) in sediments by the medium of bacteria. As the distribution of bac-teria is believed to be strongly affected by the sedimentary envi     

STUDIES ON THE RELATIONSHIP BETWEEN THE HELICAL STRUCTURE AND OPTICAL ACTIVITIES OF SOME CHIRAL CYCLICESTERS Ⅰ

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NOVEL REACTIONS BETWEEN CHROMIUM CARBYNE COMPOUNDS AND DICOBALT OCTACRBONYL

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THE RELATION BETWEEN THE DIMENSIONS OF BOUNDARY AND PHASE BOUNDARY IN ISOBARIC PHASE DIAGRAMS

The relation between the dimensions of boundary and phase boundary in isobaric phase diagrams has been proved theoretically in this paper.     

FORMATION OF THE CRYSTALLINE INCLUSION COMPLEX BETWEEN β-CYCLODEXTRIN AND POLYPROPYLENE

PP can be included in the cavities of cyclodextrin (CD). The crystalline inclusion complex between β-CD and lowmolecular weight polypropylene (PP) was obtained and investigated. α-CD and γ-CD did not form crystalline inclusioncomplexes with PP. The FTIR spectra, TGA, X-ray diffraction spectra were studied, ~1H-NMR spectra and ~(13)C CP/MAS NMR spectra were used to characterize the crystalline inclusion complexes.     

A THEORETICAL STUDY OF MECHANISMS IN THE PHOTOCHEMICAL REACTIONS OF FORMING XETENE AFTER THE α-EOND RUPTURE IN CYCLCHEMANONE

ab initio,SCF+CI calculations of the potential energy surfaces and barries in the various paths are presented for the chemical reactions of forming ketene after the a-bond rupture in cyclohexanone,using acetaldehyde as model.The possibilities of the various paths and thansition states of the important paths are discussed.