Oxidations with lead tetraacetate. V. Oxidations of 1,3-benzoxathioles

1984 ◽  
Vol 37 (6) ◽  
pp. 1255 ◽  
Author(s):  
C Aromdee ◽  
ER Cole ◽  
G Crank
Keyword(s):  
Carbon Atom ◽  
Benzene Ring ◽  
Sulfur Atom ◽  
Complex Mixture ◽  
Polymeric Materials ◽  
Lead Tetraacetate ◽  
A Minor ◽  
Minor Reaction

2,2-Disubstituted 1,3-benzoxathioles are easily oxidized by lead tetraacetate to a complex mixture of products. Acetoxylation takes place on the first carbon atom of the 2-alkyl or -cycloalkyl sub- stituent giving acetoxy derivatives. The hetero ring is also opened yielding ketones, acetoxyketones, a disulfide and polymeric materials. Oxidation at the sulfur atom appears to be a minor reaction and no products oxidized in the benzene ring are found.

scholarly journals QUANTUM-CHEMICAL STUDY OF THE REACTION MECHANISM 1,2-ETHANEDIIOL WITH 1,3-DICHLOROPROPENE

2020 ◽  
Vol 2018 (1) ◽  
pp. 56-57
Author(s):  
Elena Chirkina ◽  
Leonid Krivdin ◽  
Nikolay Korchevin
Keyword(s):  
Carbon Atom ◽  
Sulfur Atom ◽  
Density Functional ◽  
Quantum Chemical Study ◽  
Thiol Group ◽  
Chemical Study ◽  
Nucleophilic Attack ◽  
Substitution Product ◽  
Reaction Proceeds ◽  
Theoretical Mechanism

The theoretical mechanism of the interaction of 1,3-dichloropropene with 1,2- ethanedithiol in the system "hydrazine hydrate-KOH" has been proposed by the method of B3LYP / 6- 311 ++ G (d, p) in the framework of the theory of the electron-density functional according to which the reaction proceeds successively in several stages, including the nucleophilic substitution of the chlorine atom present in the sp3-hybridized carbon atom with a sulfur atom to form a mono-substitution product that undergoes a prototropic allylic rearrangement that migrates the double bond to the sulfur atom, followed by closure in the dithiolane cycle due to the nucleophilic attack of the sulfide anion of the second thiol group of the reagent per carbon atom located in the γ-position with respect to the second chlorine atom.

scholarly journals THEORETICAL STUDY OF THE REACTION MECHANISM 1,2-ETHANEDIIOL WITH 1,3-DICHLOROPROPENE

2020 ◽  
Vol 2018 (1) ◽  
pp. 68-77
Author(s):  
Elena Chirkina ◽  
Leonid Krivdin ◽  
Nikolay Korchevin
Keyword(s):  
Carbon Atom ◽  
Chlorine Atom ◽  
Sulfur Atom ◽  
Density Functional ◽  
Theoretical Study ◽  
Thiol Group ◽  
Nucleophilic Attack ◽  
Substitution Product ◽  
Reaction Proceeds ◽  
Theoretical Mechanism

The theoretical mechanism of the interaction of 1,3-dichloropropene with 1,2-ethanedithiol in the system "hydrazine hydrate-KOH" has been proposed by the method of B3LYP / 6-311 ++ G (d, p) in the framework of the theory of the electron-density functional according to which the reaction proceeds successively in several stages, including the nucleophilic substitution of the chlorine atom present in the sp3-hybridized carbon atom with a sulfur atom to form a mono-substitution product that undergoes a prototropic allylic rearrangement that migrates the double bond to the sulfur atom, followed by closure in the dithiolane cycle due to the nucleophilic attack of the sulfide anion of the second thiol group of the reagent per carbon atom located in the γ-position with respect to the second chlorine atom.

The German Labour Market Miracle

2010 ◽  
Vol 214 ◽  
pp. R38-R50 ◽  
Author(s):  
Jens Boysen-Hogrefe ◽  
Dominik Groll
Keyword(s):  
Labour Market ◽  
Minor Role ◽  
Dynamic Simulations ◽  
The Great Recession ◽  
Wage Moderation ◽  
Time Work ◽  
The Difference ◽  
A Minor ◽  
Short Time ◽  
Minor Reaction

This paper lays out the various reasons for the exceptional performance of the German labour market during and after the Great Recession of 2008/9. The reference point of our analysis is provided by an empirical model of both total hours worked and employment. We conduct dynamic simulations of the crisis period to assess how surprising the reaction of the labour market really was. We argue that the most important precondition for the minor reaction of employment during this crisis was the pronounced wage moderation observed in the years before, which constitutes a distinct difference to all other recessions in Germany. Beyond that, the flexibility of adjusting working time, which has increased considerably during the past ten years, facilitated a tendency to labour hoarding. In contrast, short-time work plays a minor role in explaining the difference from previous recessions, since this instrument has always been available to firms in Germany and its use has not been extraordinary compared with earlier recessions.

Oxidative cyclization of carbonyl derivatives. 5-Imino-Δ1-1,2,4-triazolines from alkylideneimino guanidines

1978 ◽  
Vol 56 (16) ◽  
pp. 2194-2196 ◽  
Author(s):  
Lubomira M. Cabelkova-Taguchi ◽  
John Warkentin
Keyword(s):  
Sodium Carbonate ◽  
Oxidation Product ◽  
Methylene Chloride ◽  
Oxidative Cyclization ◽  
Lead Tetraacetate ◽  
Carbonyl Derivatives ◽  
A Minor ◽  
Major Oxidation

Treatment of 2-propylideneimino guanidinium acetate with lead tetraacetate, in methylene chloride containing solid sodium carbonate, afforded the previously unknown 3,3-dimethyl-5-imino-Δ1-1,2,4-triazoline. Similarly, N,N′-diphenyl-N″-(2-propylideneimino)guanidinium acetate afforded Z-4-phenyl-5-phenylimino-Δ1-1,2,4-triazoline as the major oxidation product and the corresponding E isomer as a minor product. Stereochemistry was established spectrophotometrically and also by isomerizing the minor (E) isomer to the major (Z) isomer.

Synthesis of some bicyclo[2.2.2]oct-5-en-2-ones and bicyclo[2.2.2]octan-2-ones. Rearrangements accompanying oxidative decarboxylation with lead tetraacetate

1981 ◽  
Vol 59 (2) ◽  
pp. 344-355 ◽  
Author(s):  
Peter Yates ◽  
Gordon E. Langford
Keyword(s):  
Dicarboxylic Acid ◽  
Acyl Migration ◽  
Dicarboxylic Acids ◽  
Acid Group ◽  
Major Product ◽  
Lead Tetraacetate ◽  
Oxidative Decarboxylation ◽  
Similar Treatment ◽  
Carbonium Ion ◽  
A Minor

1-Methoxy-2-methyl-1,4-cyclohexadiene (3), 2-methoxy-1-methyl-1,3-cyclohexadiene (2), and 2-methoxy-1,5,5-trimethyl-1,3-cyclohexadiene (14) on heating with maleic anhydride give 1-methoxy-endo-7-methylbicyclo[2.2.2]oct-5-ene-syn-2,3-dicarboxylic acid anhydride (7) and its 6-methoxy-1-methyl (16a) and 6-methoxy-1,8,8-trimethyl (16b) analogues, respectively. On hydrolysis 16a and 16b give the corresponding keto dicarboxylic acids, 18a and 18b, via keto anhydrides 17a and 17b. Treatment of 18b with lead tetraacetate gives 1,8,8-trimethylbicyclo[2.2.2]oct-5-en-2-one (19) together with products in which rearrangement to a bicyclo[3.2.1]octane system has occurred. Treatment of 17b with bis(triphenylphosphino)nickel dicarbonyl gives only 19; similar treatment of 17a gives 1-methylbicyclo[2.2.2]oct-5-en-2-one (1). Reaction of bicyclo[2.2.2]octane-2,3-dione (27) with methyllithium gives 3-hydroxy-3-methylbicyclo[2.2.2]octan-2-one (28), its dimer 31, and a diol 30. Treatment of 5-exo-acetoxy-1, 5-endo-dimethyl-6-oxobicyclo[2.2.2]octane-anti-2,3-dicarboxylic acid (37) with lead tetraacetate gives 3-endo-acetoxy-1,3-exo-dimethyl-bicyclo[2.2.2]oct-5-en-2-one (33) as a minor product; the major product is derived by rearrangement to a bicyclo[3.2.1]octane system. It is proposed that this rearrangement, like that of 18b, involves oxidative decarboxylation of a single carboxylic acid group to give a carbonium ion that undergoes rearrangement via a 1,2-acyl migration.

Aril Azines. II. Hydrogenation of p-Tolil Monoazine

1975 ◽  
Vol 53 (5) ◽  
pp. 748-752 ◽  
Author(s):  
Peter Yates ◽  
E. M. Levi
Keyword(s):  
Hydrogen Atom ◽  
Carbon Atom ◽  
Sodium Borohydride ◽  
Sodium Methoxide ◽  
Major Product ◽  
Lead Tetraacetate ◽  
Ring Closure ◽  
Carbonyl Carbon Atom ◽  
Carbonyl Carbon ◽  
Independent Synthesis

Hydrogenation of p-tolil monoazine (1b) over palladium-on-charcoal gives as the major product 4,5-dihydro-5-(p-toluyl)-3,4,5-tri-(p-tolyl)-1H-pyrazol-4-ol (2b), which has previously been obtained by treatment of 1b with sodium methoxide. Several minor products are formed, which include p-tolualdehyde, p-toluic acid, and p-toluamide, p-tolunitrile, p-tolualazine, and 3,4,5-tri-(p-tolyl)-4H-pyrazo-4-ol (9). The structure of the last compound, which is also formed on reduction of 1b with sodium borohydride, was established by its independent synthesis from 1,2,3-tri-(p-tolyl)-1,3-propanedione by oxidation with lead tetraacetate followed by treatment with hydrazine. It is suggested that 2b arises via reduction of a C=N bond of 1b and aldol ring closure. The minor hydrogenation products are of interest in that their formation involves C—C hydrogenolysis; it is suggested that this is initiated by addition of a hydrogen atom to a carbonyl carbon atom of 1b.

scholarly journals Structure of a minor reaction product formed via base promoted hydrolysis of Thiele’s ester

ARKIVOC ◽  
2003 ◽  
Vol 2004 (3) ◽  
pp. 66-73 ◽  
Author(s):  
William H. Watson ◽  
Alan P. Marchand ◽  
Rasapalli Sivappa
Keyword(s):  
A Minor ◽  
Hydrolysis Of ◽  
Minor Reaction

Tris-bipyridine based dinuclear ruthenium(ii)–osmium(iii) complex dyads grafted onto TiO2 nanoparticles for mimicking the artificial photosynthetic Z-scheme

2017 ◽  
Vol 19 (6) ◽  
pp. 4778-4786 ◽  
Author(s):  
Ludovic Favereau ◽  
Abhinandan Makhal ◽  
David Provost ◽  
Yann Pellegrin ◽  
Errol Blart ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Tio2 Nanoparticles ◽  
Charge Separation ◽  
Photoinduced Electron Transfer ◽  
Reaction Pathway ◽  
System P ◽  
Dinuclear Ruthenium ◽  
Artificial Photosynthetic ◽  
A Minor ◽  
Minor Reaction

A Ru(ii)–Os(iii) dyad was grafted on TiO2 to achieve Z-scheme charge separation, but photoinduced electron transfer was shown to be a minor reaction pathway in this system.

The pyrolysis of oxindoles at 850°C

1972 ◽  
Vol 25 (1) ◽  
pp. 149 ◽  
Author(s):  
RFC Brown ◽  
M Butcher
Keyword(s):  
Mass Spectrum ◽  
Contact Time ◽  
Complex Mixture ◽  
Short Contact ◽  
Short Contact Time ◽  
13C Labelling ◽  
A Minor

Pyrolysis of oxindole at 850�C/0.7 mm with short contact time gives a complex mixture of products including benzene, benzonitrile, 2-vinylpyridine, o-toluidine, aniline, and o-aminostyrene. The pyrolysis has been investigated by using 1% and 13C labelling and by studying the effects of methyl and phenyl substituents. The nitrile carbon of benzonitrile thus formed is derived from C7a of oxindole, and not from C3. Pyrolysis of 7-phenyloxindole forms 1-methylcarbazole, and 4-phenyl-oxindole forms 1-aminofluorene. These results are interpreted in terms of the formation and subsequent rearrangement of arylnitrenes and arylcarbenes. The pyrolysis of oxindole is compared with pyrolyses of o-tolyl azide and tropyl azide. The mass spectrum of oxindole is reinterpreted in the light of the pyrolytic results; the spectrum of [3-13Cloxindole shows that loss of H13CN is a minor process (25-30%).

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