Studies in the Cycloproparene Series: The Behavior of Alkylidenecycloproparenes Towards Nucleophiles and Oxidizing Agents

1988 ◽  
Vol 41 (6) ◽  
pp. 845 ◽  
Author(s):  
SJ Buckland ◽  
B Halton ◽  
PJ Stang
Keyword(s):  
Osmium Tetroxide ◽  
Sodium Periodate ◽  
Hydroxy Ketone ◽  
Initial Formation ◽  
Oxidizing Agents

The alkylidenecycloproparene (1) reacts with potassium t- butoxide to give the ring-expanded heptafulvene (3). Epoxidation of (1) provides the hydroxy ketone (5) probably via the spiro epoxide (4) but carbene additions fail to give spirocycle (7). Photooxygenation of (1a,b) gives products (5),(12)-(14) and (16) which are explicable in terms of initial formation of dioxetan (10); products (13) and (14) result from 1H-cyclopropa[b] naphthalenone (11). By comparison (1c) provides phenanthraquinone acetal (17) in low yield. With osmium tetroxide and sodium periodate , (1a) gives benzophenone (12a) in competition with hydroxy ketone (5a) and 2,2-diphenylcyclobutanaphthalenone (20). The modes of formation of the various products are discussed.

Synthesis of 17β-[4-(1,3-thiazolyl)]androstane 3β-hemisuccinate and glycoside

1984 ◽  
Vol 49 (4) ◽  
pp. 1039-1050 ◽  
Author(s):  
Pavel Drašar ◽  
Vladimír Pouzar ◽  
Ivan Černý ◽  
Jorga Smolíková ◽  
Miroslav Havel
Keyword(s):  
Osmium Tetroxide ◽  
Hydroxy Ketone ◽  
Hantzsch Reaction ◽  
Bromo Derivative

The protected 20(21)-en-20-ol ether III was oxidized with N-methylmorpholine N-oxide monohydrate and osmium tetroxide to give the hydroxy ketone IV which was converted into the bromo derivative VIII via the mesylate VI. Hantzsch reaction of the bromo ketone VIII with ethyl thioxamate afforded the thiazole XI whose hemisuccinate XIII and glycoside XV were prepared.

Methane Oxidation by Aqueous Osmium Tetroxide and Sodium Periodate: Inhibition of Methanol Oxidation by Methane

2006 ◽  
Vol 45 (44) ◽  
pp. 7433-7436 ◽  
Author(s):  
Takao Osako ◽  
Eric J. Watson ◽  
Ahmad Dehestani ◽  
Brian C. Bales ◽  
James M. Mayer
Keyword(s):  
Methane Oxidation ◽  
Methanol Oxidation ◽  
Osmium Tetroxide ◽  
Sodium Periodate

scholarly journals Pretreating Epoxy Thin Sections With Sodium Periodate Prior To Immunostaining

1997 ◽  
Vol 5 (6) ◽  
pp. 24-25 ◽  
Author(s):  
Hildegard H. Crowley
Keyword(s):  
Hydrogen Peroxide ◽  
Surface Layer ◽  
Electron Density ◽  
Sodium Methoxide ◽  
Sodium Periodate ◽  
Thin Sections ◽  
Oxidizing Agents ◽  
Antigenic Sites

Pretreatment of epoxy thin sections with strong oxidizing agents such as hydrogen peroxide, sodium methoxide, and sodium m-metaperiodate facilities the location of antigens with immunostaining procedures. Etching, or pretreatment, of sections unmasks antigenic sites on glutaraldehyde fixed and postosmicated tissue, partially removes osmium bonds, temporarily decreases the hydrophobicity of the epoxy surface layer of the section, reduces the electron density of the tissue and increases resistance to heavy rnetai poststaining.

ChemInform Abstract: Cleavage of Olefins (I) by Polymer-Supported Osmium Tetroxide and Sodium Periodate.

ChemInform ◽  
1989 ◽  
Vol 20 (23) ◽  
Author(s):  
G. CAINELLI ◽  
M. CONTENTO ◽  
F. MANESCALCHI ◽  
L. PLESSI
Keyword(s):  
Osmium Tetroxide ◽  
Sodium Periodate ◽  
Polymer Supported

Cleavage of Olefins by Polymer-Supported Osmium Tetroxide and Sodium Periodate

Synthesis ◽  
1989 ◽  
Vol 1989 (01) ◽  
pp. 47-48 ◽  
Author(s):  
Gianfranco Cainelli ◽  
Michele Contento ◽  
Francesco Manescalchi ◽  
Laura Plessi
Keyword(s):  
Osmium Tetroxide ◽  
Sodium Periodate ◽  
Polymer Supported

Synthesis and antiviral activity of stereoisomeric eritadenines

1982 ◽  
Vol 47 (5) ◽  
pp. 1392-1407 ◽  
Author(s):  
Antonín Holý ◽  
Ivan Votruba ◽  
Erik De Clercq
Keyword(s):  
Antiviral Activity ◽  
Acid Hydrolysis ◽  
Vesicular Stomatitis Virus ◽  
Sodium Borohydride ◽  
Osmium Tetroxide ◽  
Sodium Periodate ◽  
Parainfluenza Virus ◽  
Racemic Mixture ◽  
Isopropylidene Derivative ◽  
Vesicular Stomatitis

D-Eritadenine (Ia) and L-eritadenine (IIa) were prepared from 5-(adenin-9-yl)-5-deoxyaldofuranoses or enantiomeric 2,3-disubstituted erythronolactones (VIIIb, c, XIV). Oxidation of methyl 2,3-O-isopropylidene-D-ribofuranoside (IX) with periodate in the presence of ruthenium, followed by acid hydrolysis and reduction with sodium borohydride, afforded L-ribonolactone (XI). Its 2,3-O-isopropylidene derivative was subjected to alkaline hydrolysis, followed by oxidation with periodate, reduction with sodium borohydride and reaction with cyclohexanone to give 2,3-O-cyclohexylidene-L-erythronolactone (XIV). Condensation of [U-14C]-adenine with VIIIb, followed by acid hydrolysis, afforded [U-14C-adenine]-D-eritadenine. The threo-eritadenines III and IV were prepared by oxidation of 1-(adenin-9-yl)-1-deoxy-2,3-O-isopropylidenethreitols XVI and XVII with sodium periodate in the presence of ruthenium, followed by acid hydrolysis. Reaction of 9-(2,2-diethoxyethyl)adenine (XIX) with malonic acid gave 4-(adenin-9-yl)-3-butenoic acid (XXI); its methyl ester XXII, prepared by treatment with methanol, was isomerized with triethylamine to give methyl 4-(adenin-9-yl)-2-butenoate (XXIII). Hydroxylation of XXIII with osmium tetroxide afforded the racemic mixture of D- and L-threo-eritadenine (III+ IV). Eritadenines Ia and IIa were active against vaccinia, measles and vesicular stomatitis virus. Eritadenine Ia was also effective against reo- and parainfluenza virus. In general, the antiviral activity of the eritadenines decreased in the order D-erythro (Ia) > L-erythro (IIa) > D- and L-threo (III, IV).

Methane Oxidation by Aqueous Osmium Tetroxide and Sodium Periodate: Inhibition of Methanol Oxidation by Methane

2006 ◽  
Vol 118 (44) ◽  
pp. 7593-7596 ◽  
Author(s):  
Takao Osako ◽  
Eric J. Watson ◽  
Ahmad Dehestani ◽  
Brian C. Bales ◽  
James M. Mayer
Keyword(s):  
Methane Oxidation ◽  
Methanol Oxidation ◽  
Osmium Tetroxide ◽  
Sodium Periodate

Periodate Treatment and “All-or-None” Dehydrogenase Staining Phenomena

1968 ◽  
Vol 26 ◽  
pp. 12-13
Author(s):  
C. G. Rosa
Keyword(s):  
Mitochondrial Membrane ◽  
Osmium Tetroxide ◽  
Sodium Periodate ◽  
Staining Pattern ◽  
Succinic Dehydrogenase ◽  
Positive Contrast ◽  
Uranyl Acetate ◽  
Middle Piece ◽  
Periodate Treatment ◽  
Membrane Stabilizer

It has been shown that when suspensions of fresh rodent sperm are incubated in the presence of tetranitro-blue tetrazolium (TNBT) and stained for succinic dehydrogenase (SDH),this enzyme is localized in the mitochondria of the middle-piece. Rat and mouse spermatozoa treated in this manner and postfixed (suspension) in 4°C Millonig's osmium tetroxide for brief periods demonstrate SDH reactivity in mitochondrial profiles that indicate no SDH, almost complete activity, or most commonly, intermediate staining reactions in the internal membranes (Figure 1). In the last instance, the cristal membranes display a heterogeneous formazan (reduced TNBT) staining pattern not in agreement with the Seligman “all-or-none” hypothesis concerning mitochondrial oxidative enzymatic reactivity.In order to test this hypothesis and circumvent some of the attendant difficulties in these procedures (penetration of reaction mixture components, fixatives), all cytochemical reactions and postfixation were performed on suspensions of sperm from the cauda epididymides of mature rats. An attempt was made to divorce electron densities due to osmium postfixation by employing 1% aqueous sodium periodate (pH 3-4) as a mitochondrial membrane stabilizer through the embedding procedures. Previous use of this treatment allowed preservation of the membranes of these organelles in positive contrast as evidenced by uranyl acetate staining of sectioned material (Figures 2 & 3).

Synthesis of 4-(21-nor-5-pregnen-20-yl)-1,3-thiazole derivatives

1984 ◽  
Vol 49 (4) ◽  
pp. 1051-1059 ◽  
Author(s):  
Pavel Drašar ◽  
Vladimír Pouzar ◽  
Ivan Černý ◽  
Miroslav Havel
Keyword(s):  
Osmium Tetroxide ◽  
Hydroxy Ketone ◽  
Hantzsch Reaction ◽  
Enol Ether ◽  
Thiazole Derivatives ◽  
Silyl Enol Ether

The keto sulfoxide IV, prepared from the ester III, was reduced with amalgamated aluminium to give the ketone V which after enolization and silylation afforded the silyl enol ether VI. Oxidation of VI with osmium tetroxide and N-methylmorpholine N-oxide monohydrate yielded the α-hydroxy ketone VII. This was converted into the mesylate IX and further into the bromo ketone XI which on Hantzsch reaction with ethyl thioxamate furnished the steroidal thiazole XII. Compound XII was converted into the hemisuccinate XIV.

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