ChemInform Abstract: SYNTHESIS VIA PUMMERER INTERMEDIATES. III. REARRANGEMENTS OF 3-(METHYLSULFINYL)QUINOLINONES, 3-(METHYLSULFINYL)CINNOLINONES, 3-(METHYLSULFINYL)CHROMANONES AND 3-(METHYLSULFINYL)CHROMONES WITH ACETIC ANHYDRIDE AND WITH THIONYL CHLORIDE

1978 ◽  
Vol 9 (33) ◽  
Author(s):  
D. T. CONNOR ◽  
P. A. YOUNG ◽  
M. VON STRANDTMANN
Keyword(s):  
Acetic Anhydride ◽  
Thionyl Chloride

Chemistry of Fenchonesulfonic Acid Derivatives

1995 ◽  
Vol 50 (2) ◽  
pp. 283-288 ◽  
Author(s):  
Gabriele Wagner ◽  
Uwe Verfürth ◽  
Rudolf Herrmann
Keyword(s):  
Acetic Anhydride ◽  
Thionyl Chloride ◽  
Sulfonic Acid ◽  
Reaction Rate ◽  
Enantiomeric Excess ◽  
Methyl Group ◽  
Close Analogy ◽  
Chiral Sulfoxides ◽  
Mndo Calculations ◽  
Nmr Techniques

(1 S) - (+)-Fenchone is sulfonated by SO3 or H2SO4/acetic anhydride in the bridgehead methyl group. This could be confirmed by NMR techniques (INADEQUATE). The fenchonesulfonic acid obtained is converted (SOCl2/NH3) to the cyclic fenchonesulfonimide, which can be oxidized to the corresponding oxaziridine, in close analogy to 10-camphorsulfonimide. Improved procedures for this reaction sequences are given. During the treatment of the sulfonic acid with thionyl chloride, a byproduct with a rearranged bicyclic skeleton is observed whose structure has been determined by ozonolytic degradation and NMR techniques. A possible mechanism for this rearrangement is suggested, based on MNDO calculations of the intermediate carbocations. The fenchonesulfonyloxaziridine oxidizes sulfides to chiral sulfoxides with appreciable enantiomeric excess, but very low reaction rate. A comparison with camphor-derived oxaziridines having similar steric requirements is made.

Synthesis of 5-Phenylcytosine Nucleoside Derivatives

1996 ◽  
Vol 61 (4) ◽  
pp. 645-655 ◽  
Author(s):  
Marcela Krečmerová ◽  
Hubert Hřebabecký ◽  
Antonín Holý
Keyword(s):  
Acetic Anhydride ◽  
Thionyl Chloride ◽  
Alkaline Hydrolysis ◽  
Hydrogen Bromide ◽  
Analogous Reaction ◽  
Final Reaction Product ◽  
Cyclic Sulfite ◽  
Higher Temperature ◽  
Hydrolysis Of ◽  
Tin Tetrachloride

Reaction of silylated 5-phenylcytosine with 1-O-acetyl-2,3,5-tri-O-benzoyl-D-ribose, catalyzed with tin tetrachloride, and subsequent methanolysis afforded 5-phenylcytidine (2). This compound reacted with thionyl chloride in acetonitrile to give cyclic sulfite 3 which on heating in dimethylformamide was converted into 2,2'-anhydro-1-(β-D-arabinofuranosyl)-5-phenylcytosine (4). Analogous reaction of compound 2 with thionyl chloride at reflux gave 5'-chloro-5'-deoxy-2',3'-cyclic sulfite 5. Its heating in dimethylformamide afforded 5'-chloro-2,2'-anhydro derivative 6, mild alkaline hydrolysis led to 5'-chloro-5'-deoxy-5-phenylcytidine (7). Alkaline hydrolysis of 5-phenyl-2,2'-anhydrocytidine (4) gave 5-phenylcytosine arabinoside 8, whereas the 2,2'-anhydro derivative 6 afforded 1-(5-chloro-5-deoxy-β-D-arabinofuranosyl)-5-phenylcytosine (11). At higher temperature, the final reaction product was 2,5'-anhydro-5-phenylcytidine (12). 5'-Chloro-5'-deoxynucleosides 7 and 11 reacted with tri-n-butyl- stannane to give 5'-deoxyribofuranosyl and 5'-deoxyarabinofuranosyl derivatives 15 and 16. 5-Phenylcytidine (2) was converted into the N4-acetate 17 with acetic anhydride. Further reaction with acetic anhydride and hydrogen bromide in acetic acid afforded a mixture of peracetylated 2'-bromo and 3'-bromo derivatives 18 and 19. Reaction with Zn/Cu couple gave 5'-O-acetyl-5-phenyl-2',3'-didehydro derivative 20 and 2',3',5'-tri-O-acetyl-5-phenylcytidine (21). Compound 20 was deblocked to 1-(2,3-dideoxy-β-D-glycero-pent-2-enofuranosyl)-5-phenylcytosine (22). Catalytic hydrogenation of compound 20 over palladium and subsequent deblocking of the protected 2',3'-dideoxy derivative 23 gave 1-(2,3-dideoxy-β-D-glycero-pentofuranosyl)-5-phenylcytosine (24).

2',3'-Dideoxy- and 3'-Azido-2',3'-dideoxynucleosides of 5-Phenyl-2(1H)-pyrimidinone. Preparation of 2',3'-Dideoxypentofuranoses

1996 ◽  
Vol 61 (3) ◽  
pp. 478-488 ◽  
Author(s):  
Marcela Krečmerová ◽  
Hubert Hřebabecký ◽  
Milena Masojídková ◽  
Antonín Holý
Keyword(s):  
Acetic Anhydride ◽  
Thionyl Chloride ◽  
Benzoyl Chloride ◽  
Chromium Trioxide ◽  
Minor Amount ◽  
Subsequent Reduction ◽  
Silyl Derivative ◽  
Chloro Derivative ◽  
Trimethylsilyl Trifluoromethanesulfonate ◽  
Keto Derivative

The synthesis of methyl 3-azido-5-benzoyl-2,3-dideoxy-β-D-ribofuranoside (10) from methyl 2-deoxy-D-ribofuranoside (1) and its use for the preparation of 3'-azido-2',3'-dideoxy-β-D-ribofuranosides is described. Reaction of methylglucoside 1 with benzoyl chloride in pyridine afforded 5-O-benzoyl derivative 2, which on oxidation with complex of chromium trioxide, pyridine and acetic anhydride afforded 3-keto derivative 3. This was reduced with sodium borohydride in ethanol to give a mixture of methyl 2-deoxyglycosides of α-D-ribo- (4) and β-D-xylo- (5) configuration. Their mesyl derivatives 6 and 7 were chromatographically separated. Compound 7 reacted with sodium azide in hot dimethylformamide to afford methyl 3-azido-5-O-benzoyl-2,3-dideoxy-β-D-ribofuranoside (10). 5-Phenyl-2(1H)-pyrimidinone was converted into silyl derivative 11 by treatment with hexamethyldisilazane. Reaction of compound 11 with the azido sugar 10, catalyzed by trimethylsilyl trifluoromethanesulfonate, and subsequent methanolysis, furnished a mixture of anomeric 3'-azido-2',3'-dideoxynucleosides 14 and 15. Methyl 5-O-benzoyl-2,3-dideoxy-α-D-ribofuranoside (17) was prepared from methyl-α-glycoside 4 by reaction with thionyl chloride and subsequent reduction of the obtained 3-chloro derivative 16 with tributylstannane. Silyl derivative 11 reacted with 2,3-dideoxy sugar 17 under catalysis with trimethylsilyl triflate to give mainly 1-(5-O-benzoyl-2,3-dideoxy-α-D-glycero-pentofuranosyl)-5-phenyl-2(1H)-pyrimidinone (19) and minor amount of the β-anomer 18. Their methanolysis afforded dideoxynucleosides 20 and 21.

Reactions of 5-Hydroxy steroids. XIII. The acid-catalysed reactions of Cholestane-4,5-diol 4-acetates and Cholestane-4,5-diol diacetates

1974 ◽  
Vol 27 (7) ◽  
pp. 1505 ◽  
Author(s):  
ETJ Bathurst ◽  
JM Coxon ◽  
MP Hartshorn
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Sulphuric Acid ◽  
Thionyl Chloride ◽  
Effect Of Substituents ◽  
Carbonium Ion ◽  
Rearrangement Process ◽  
Acid Catalysed Reactions

The reaction of 5α-cholestane-4α,5-diol 4-acetate (lb) with sulphuric acid-acetic anhydride-acetic acid occurs almost exclusively by loss of the 6α-proton to give cholest-5-en-4a-yl acetate (3) while dehydration with thionyl chloride-pyridine occurs predominantly (c. 80%) by loss of the 6β-proton. On reaction with D2SO4-DOAc-Ac2O, 5α-cholestane-4β,5-diol 4-acetate (7) undergoes backbone rearrangement to give olefins (9),(10) and (11) without incorporation of deuterium and thus excludes the intermediacy of olefins and cyclopropanes in the rearrangement process. The effect of substituents on these reactions has been rationalized by consideration of the initial conformation of the C5 carbonium ion.

Synthesis and Estrogenic Activity Screening of Some 6,9-Disubstituted Estradiol Derivatives

2005 ◽  
Vol 70 (4) ◽  
pp. 479-486 ◽  
Author(s):  
Marija N. Sakač ◽  
Katarina M. Penov Gaši ◽  
Mirjana Popsavin ◽  
Evgenija A. Djurendić ◽  
Silvana Andrić ◽  
...  
Keyword(s):  
Acetic Anhydride ◽  
Sodium Borohydride ◽  
Thionyl Chloride ◽  
Estrogenic Activity ◽  
Chromium Vi ◽  
Antiestrogenic Activity ◽  
Estradiol Derivatives ◽  
Biological Tests ◽  
Activity Screening

Oxidation of estradiol dipropionate (1) with chromium(VI) oxide-3,5-dimethylpyrazole complex yielded 9α-hydroxy-6-oxoestra-1,3,5(10)-triene-3,17β-diyl dipropionate (2) and 6-oxoestra-1,3,5(10)-triene-3,17β-diyl dipropionate (3). Dehydration of compound 2 with phosphorus(V) oxide or acetic anhydride gave 6-oxoestra-1,3,5(10),9(11)-tetraene-3,17β-diyl dipropionate (5). Reduction of compounds 2 and 5 with sodium borohydride afforded 3,6β,9α-trihydroxyestra-1,3,5(10)-triene-17β-yl propionate (4) and 3,6β-dihydroxyestra-1,3,5(10),9(11)-tetraene-17β-yl propionate (6), respectively. The action of thionyl chloride on compound 2 yielded 6-hydroxyestra-1,3,5(10),6,8-pentaene-3,17β-diyl dipropionate (7). Biological tests in vivo of these compounds showed a moderate antiestrogenic activity of compound 4.

DETERMINATION OF ALDOSTERONE AND DEOXYCORTICOSTERONE IN PLASMA USING 3H-ACETIC ANHYDRIDE AND VAPOUR PHASE ACETYLATION

1969 ◽  
Vol 61 (1_Suppl) ◽  
pp. S12 ◽  
Author(s):  
V. H. T. James ◽  
A. E. Rippon ◽  
M. L. Arnold
Keyword(s):  
Acetic Anhydride ◽  
Vapour Phase

Syntheses and Cytotoxicity Screening of some Novel 1,2,4-Triazine Derivatives against Liver Carcinoma Cell Lines

2020 ◽  
Vol 17 ◽  
Author(s):  
W. Abd El-Fattah
Keyword(s):  
Acetic Anhydride ◽  
Cell Lines ◽  
Carcinoma Cell ◽  
Aromatic Aldehydes ◽  
Liver Carcinoma ◽  
Anticancer Activities ◽  
Carcinoma Cell Lines ◽  
Elemental Analyses ◽  
Triazine Derivatives ◽  
C Nmr

: In this work, 1,2,4-triazine derivatives were synthesized and evaluated for anticancer activities. Series of 1,2,4-triazine derivatives (4a, b) were prepared via the reaction of N-benzoyl glycine (1) with aromatic aldehydes in presence of fused sodium acetate and acetic anhydride to give 1,3-oxazolinone derivatives (2a, b), followed by condensation with 1-(ethoxycarbonyl) hydrazine (3) in glacial acetic acid. Compounds (4a, b) then reacted with acetic anhydride, ethyl chloroacetate and 2,4-dinitrophenyl hydrazine yielded the corresponding to N-acetyl derivatives (5a, b), N-(ethoxycarbonyl) methyl derivative (6) and 1,2-disubstituted hydrazine (7), respectively. The structures of the 1,2,4-triazine derivatives were confirmed by IR, 1H, 13C NMR, MS and elemental analyses. Anticancer activity of some 1,2,4-triazine derivatives (4-7) have been investigated. The results revealed that compounds 4a (IC50= 2.7μM), 5a (IC50= 1.5μM), and 5b (IC50= 3.9μM) show promising inhibitory growth efficacy compared to a standard antitumor drug (IC50= 4.6μM). These three compounds can be considered as potential agents against human hepatocellular carcinoma cell lines (HepG-2).

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