Synthetic use of the ribosyl derivatives of 2,4- and 2,5-thiazolidinediones

1979 ◽  
Vol 44 (5) ◽  
pp. 1475-1482 ◽  
Author(s):  
Hubert Hřebabecký ◽  
Zdeněk Točík ◽  
Jiří Beránek
Keyword(s):  
Hydrazine Hydrate ◽  
Hydrogen Chloride ◽  
Sodium Methoxide ◽  
Aqueous Ammonia ◽  
Hydroxylamine Hydrochloride ◽  
Acetyl Derivative ◽  
High Yield ◽  
Derivatives Of ◽  
Methanolic Ammonia

On ribosidation of 2,4-thiazolidinedione (2,5-thiazolidinedione, respectively), the 3-β-D-ribofuranosyl derivative is formed in high yield, either the benzoyl derivative Ia (IIa) or the acetyl derivative Ib (IIb). The unsubstituted ribosyl derivative Ic is formed from the acetyl derivative Ib by methanolic hydrogen chloride. The benzoylated ribosyl-2,4-thiazolidinedione Ia affords the benzoylated ribosylurea III on reaction with aqueous ammonia, the hydroxyethylurea derivative IVa with 2-aminoethanol, the semicarbazide derivative Va with hydrazine hydrate, the ribosylhydroxyurea derivative VIa on reaction with hydroxylamine hydrochloride and triethylamine, the benzoyl derivative of ribosylbiuret VII with O-methylisourea hydrochloride and triethylamine, and (analogously) ribosylisothiobiuret VIII with S-methylisothiourea. Methanolysis of the benzoyl derivative of hydroxyethylurea IVa with sodium methoxide affords the unprotected riboside IVb. Ribosylhydroxyurea VIb is formed on debenzoylation of compound VIa with methanolic ammonia. Acetylation of compound VIb furnishes the pentaacetyl derivative VIc.

New Route Synthesis of Styryl Pyrones: High Yield Synthesis, Reactions and Spectral Properties of 2-Phenyl-6-Styryl-4-Pyrones

2005 ◽  
Vol 2005 (10) ◽  
pp. 654-656 ◽  
Author(s):  
Abdel Moneim El-Ghanam
Keyword(s):  
Hydrazine Hydrate ◽  
Spectral Properties ◽  
Sodium Ethoxide ◽  
Hydroxylamine Hydrochloride ◽  
The Other ◽  
High Yield ◽  
Phosphorus Pentasulfide ◽  
Other Hand ◽  
Synthesis Reactions ◽  
Derivatives Of

2-Phenyl-6-styryl-4-pyrone derivatives have been synthesised from the reaction of ethyl phenylpropiolate with benzylideneacetone derivatives in the presence of sodium ethoxide. Treatment of styrylpyrone with phosphorus pentasulfide gave the corresponding styrylpyran-4-thione which on treatment with hydroxylamine hydrochloride and aqueous methylamine afforded the corresponding oxime and 1-methyl-2-phenyl-6-styrylpyridine-4(1H)-thione, respectively. On the other hand, styrylpyran-4-thione reacted with malononitrile to give pyrolylidenemalononitrile which on treatment with bidentate reagents, hydrazine hydrate, hydroxylamine hydrochloride, thiourea, and thiosemicarbazide afforded the corresponding styrylspiropyran derivatives of pyrazole, 1,2-oxazole or 1,3-thiazine, respectively.

Preparation of Chloro and Sulfanyl Derivatives of 1-(2-Deoxy-4-C-hydroxymethyl-α-L-threo-Pentofuranosyl)uracil

1997 ◽  
Vol 62 (7) ◽  
pp. 1114-1127 ◽  
Author(s):  
Hubert Hřebabecký ◽  
Jan Balzarini ◽  
Antonín Holý
Keyword(s):  
Nucleophilic Substitution ◽  
Hydrogen Chloride ◽  
Thionyl Chloride ◽  
Sodium Methoxide ◽  
Thioacetic Acid ◽  
Uracil Derivatives ◽  
Derivatives Of ◽  
Hiv 1

3'-Chloro and 3'-acetylsulfanyl derivatives of 1-(2-deoxy-4-C-hydroxymethyl-α-L-threo-pentofuranosyl)uracil were prepared by reaction of 2,3'-anhydro-1-{5'-O-benzoyl-4'-C-[(benzoyloxy)methyl]-2'-deoxy-α-L-erythro-pentofuranosyl}uracil (3) with hydrogen chloride and thioacetic acid, respectively. The reaction with hydrogen chloride gave a mixture of N-1 and N-3 substituted uracil derivatives 12 and 14. Reaction of 1-{3-O-benzoyl-4-C-[(benzoyloxy)methyl]-2-deoxy-α-L-threo-pentofuranosyl}uracil (7) with thionyl chloride and subsequent debenzoylation afforded 1-(4-C-chloromethyl-2-deoxy-β-D-erythro-pentofuranosyl)uracil (19). Nucleophilic substitution with lithium thioacetate, followed by deacylation, converted 1-{3-O-benzoyl-4-C-[(benzoyloxy)methyl]-2-deoxy-5-O-p-toluenesulfonyl-α-L-threo-pentofuranosyl}uracil (9) into 1-(2-deoxy-4-C-sulfanylmethyl-β-D-erythro-pentofuranosyl)uracil (21). The obtained thiols were oxidized with iodine or air to give 1,1'-[disulfandiylbis(2,3-dideoxy-4-hydroxymethyl-α-L-threo-pentofuranose-3,1-diyl]di(pyrimidine-2,4-(1H,3H)-dione) (17) and 1,1'-[disulfandiylbis(2,5-dideoxy-4-hydroxymethyl-α-L-threo-pentofuranose-5,1-diyl]di(pyrimidine-2,4(1H,3H)-dione) (22). Reaction of 1-{3-acetylsulfanyl-5-O-methanesulfonyl-4-C-[(benzoyloxy)methyl]-2,3-dideoxy-α-L-threo-pentofuranosyl)}uracil (24) with methanolic sodium methoxide afforded 1-(3,5-anhydro-2,3-dideoxy-4-C-hydroxymethyl-3-sulfanyl-α-L-threo-pentofuranosyl)uracil (25). The same reagent was used in the preparation of 1-(3,5-anhydro-2-deoxy-4-C-hydroxymethyl-α-L-threo-pentofuranosyl)uracil (26) from 1-{4-C-[(benzoyloxy)methyl]-2-deoxy-5-O-p-toluenesulfonyl-α-L-threo-pentofuranosyl}uracil (8). From the series of 4'-substituted 2'-deoxyuridine derivatives, synthesized in this study, solely the 4'-chloromethyl derivative 19 and the oxetane derivative 26 exhibited an appreciable activity against HIV-1 and HIV-2.

Partial hydrolysis of acyl 1,6-anhydro-β-D-glucopyranose

1984 ◽  
Vol 49 (8) ◽  
pp. 1780-1787 ◽  
Author(s):  
Štefan Kučár ◽  
Juraj Zámocký ◽  
Juraj Zemek ◽  
Dušan Anderle ◽  
Mária Matulová
Keyword(s):  
Acid Hydrolysis ◽  
Hydrazine Hydrate ◽  
Hydrogen Chloride ◽  
Ester Group ◽  
The Other ◽  
Hydroxyl Group ◽  
Partial Hydrolysis ◽  
Substantial Influence ◽  
Hydrolysis Of ◽  
Derivatives Of

Partial hydrolysis of per-O-acetyl- and per-O-benzoyl derivatives of 1,6-anhydro-β-D-glucopyranose with methanolic hydrogen chloride and hydrazine hydrate was investigated. The acyl group at C(3) is of substantial influence on the course of hydrolysis. The esterified hydroxyl group at C(3) was found to be most stable on acid hydrolysis with methanolic hydrogen chloride when compared with that at C(2), or C(4); on the other hand, this ester group is the most labile upon hydrolysis with hydrazine hydrate. Selectivity of the respective ester groups towards hydrolysis made it possible to prepare all variations of acetyl and benzoyl derivatives of 1,6-anhydro-β-D-glucopyranose.

Synthesis of 2-amino-2-deoxy-D-talose and 2-amino-2-deoxy-D-galactose

1968 ◽  
Vol 46 (15) ◽  
pp. 2481-2484 ◽  
Author(s):  
M. B. Perry ◽  
Ann C. Webb
Keyword(s):  
Hydrochloric Acid ◽  
Sodium Methoxide ◽  
Ammonia Solution ◽  
Nef Reaction ◽  
Derivatives Of ◽  
Methanolic Ammonia

Treatment of D-lyxose with nitromethane in the presence of sodium methoxide gave 1-deoxy-1-nitro-D-galactitol which, after conversion to 2,3,4,5,6-penta-O-acetyl-1-deoxy-1-nitro-D-galactitol, reacted with saturated methanolic ammonia solution to yield 2-acetamido-1,2-dideoxy-1-nitro-D-talitol and 2-acetamido-1,2-dideoxy-1-nitro-D-galactitol. 2-Acetamido-1,2-dideoxy-1-nitro-D-talitol and 2-acetamido-1,2-dideoxy-1-nitro-D-galactitol were converted by a modified Nef reaction to 2-acetamido-2-deoxy-D-talose and 2-acetamido-2-deoxy-D-galactose which on hydrolysis with hydrochloric acid afforded 2-amino-2-deoxy-D-talose hydrochloride and 2-amino-2-deoxy-D-galactose hydrochloride. The properties and derivatives of the aminoglycoses are described.

Regiospecific Syntheses of the Monomethylated 3-Phenyldihydro-1,2,4-triazin-6(1H)-ones

1996 ◽  
Vol 49 (4) ◽  
pp. 463 ◽  
Author(s):  
DJ Collins ◽  
TC Hughes ◽  
WM Johnson
Keyword(s):  
Hydrazine Hydrate ◽  
Sodium Methoxide ◽  
Methyl Derivative ◽  
Nitrile Imine ◽  
Derivatives Of

Unambiguous syntheses of four unreported monomethylated derivatives of 3-phenyldihydro-1,2,4-triazin-6(1H)-ones, namely, the 1-methyl (2), 2-methyl (3), 4-methyl (4) and the imidic O-methyl derivative (5), are described. Regioselectivity was achieved for the synthesis of (2) by addition of ethyl glycinate to the 1,3-dipolar nitrile imine derived from N- methylbenzohydrazonoyl bromide hydrobromide (8). The key step for the synthesis of (3) was addition of benzyl 3-methylcarbazate (14) to ethyl N-[ chloro (phenyl) methylene ] glycinate (15b). The 4-methyl compound (4) was prepared by cycloaddition of ethyl N-( thiobenzoyl ) sarcosinate (21) with hydrazine hydrate, and the O-methyl compound (5) was prepared by reaction of sodium methoxide with 6-chloro-3-phenyl-4,5-dihydro-1,2,4-triazine (23).

5-, 6- And 7-substitution derivatives of 7-oxo-7H-benzo(c)fluorene

1982 ◽  
Vol 47 (4) ◽  
pp. 1258-1266 ◽  
Author(s):  
Jiří Křepelka ◽  
Jiří Roubík ◽  
Jiří Holubek ◽  
Iva Vančurová
Keyword(s):  
Acetyl Chloride ◽  
Hydroxylamine Hydrochloride ◽  
Acetyl Derivative ◽  
Ring Closure ◽  
Substitution Reactions ◽  
Acyl Chlorides ◽  
Chloride Method ◽  
Derivatives Of ◽  
Sole Product ◽  
Intramolecular Ring

Intramolecular ring closure of anhydrides IIa-IIc, under conditions of the Friedel-Crafts reaction, gave 6-carboxy derivatives III-V. Esterification of the acid V by the chloride method led to esters VI and VII. Reaction of the ester VI with hydrazine gave rise to compound XXI, having a pentacyclic structure. Alkylation or acylation of the 5-hydroxy group in compounds Ia-Ic with alkyl halides or acyl chlorides afforded compounds VIII-XIII and XVIII. Compound XI was also formed as a by-product in the Friedel-Crafts reaction of compound Ic with acetyl chloride in 1,2-dichloroethane, in addition to the 6-acetyl derivative XV. An analogous reaction of Ic with dichloracetyl chloride gave compound XIV as a sole product. Substitution reactions on the 7-oxo group in Ic afforded semicarbazone XVI and thiosemicarbazone XVII, and reaction of the compound XVIII with hydroxylamine hydrochloride gave the oxime XIX. The action of N-methylolchloracetamide on Ia in sulphuric acid produced compound XX. The compounds prepared proved to have no antineoplastic effects. In tests for activity against the viruses of vaccinia and encephalomyocarditis they proved to be weaker than Tiloron as control. In assessing the efficacy against influenza virus A2 Singapore compound V exhibited the same effect as Tiloron.

Asymmetric induction in the Sommelet rearrangement of chiral benzyl sulfonium salts

1976 ◽  
Vol 54 (2) ◽  
pp. 193-201 ◽  
Author(s):  
Stewart John Campbell ◽  
David Darwish
Keyword(s):  
Sodium Methoxide ◽  
Room Temperature ◽  
Exchange Resin ◽  
Shift Reagent ◽  
Asymmetric Induction ◽  
High Yield ◽  
Sulfonium Salts ◽  
Sodium Methoxide Solution ◽  
Derivatives Of ◽  
Sulfone Derivatives

The Sommelet rearrangement of (+)-ethylmethyl-p-nitrobenzylsulfonium perchlorate, (+)-1, and (+)-ethylmethyl-p-chlorobenzylsulfonium perchlorate, (+)-2, are described. Elution of (+)-1 through an hydroxide exchange resin generated ethylmethylsulfonium p-nitro-benzylide (+)-3 which decomposed in methanol at room temperature to ethyl 2-methyl-5-nitro-benzyl sulfide, 6, and (+)-methyl α-(2-methyl-5-nitrophenyl)ethyl sulfide, (+)-7, with 18 to 20.3% asymmetric induction. Decomposition of (+)-2 in sodium methoxide solution at 70 °C for 2 h produced ethyl 2-methyl-5-chlorobenzyl sulfide, 8, and (+)-methyl α-(2-methyl-5-nitro-phenyl)ethyl sulfide, (+)-9, with 21 to 25.5% asymmetric induction. The lower estimates of asymmetric induction for each sulfide were made by comparison with specific rotations of authentic samples obtained by synthesis and resolution. The higher estimates were obtained by the use of a chiral lanthanide shift reagent Eu(hfbc)3 with the sulfone derivatives of these chiral sulfides. The ylide (+)-3 reacted with aldehydes in high yield to produce oxiranes with no induction of asymmetry.

Chemistry of the Podocarpaceae. XLV. Heterocyclic derivatives of 12-Hydroxypodocarpa-8,11,13-trien-19-oic acid

1973 ◽  
Vol 26 (8) ◽  
pp. 1763 ◽  
Author(s):  
GD Beresford ◽  
RC Cambie ◽  
KP Mathai
Keyword(s):  
Hydrazine Hydrate ◽  
Hydroxylamine Hydrochloride ◽  
Heterocyclic Derivatives ◽  
Derivatives Of

The preparation of chromone (11), methylbenzoxazole (18), methylbenzisoxazole (17), flavonoid (12), and benzofuran (19) derivatives from 12-hydroxypodocarpa-8,11,13-trien-19-oic acid (1) is reported. Treatment of the chromone (11) with hydrazine hydrate affords the 3?-phenylpyrazole (20) while treatment with hydroxylamine hydrochloride affords the 3?-phenylisoxazole (21).

scholarly journals Synthesis of acylic derivatives of prolylleucylglycinamide

2019 ◽  
Vol 55 (4) ◽  
pp. 429-435
Author(s):  
V. A. Haidukevich ◽  
S. K. Petkevich ◽  
E. G. Karankevich ◽  
P. V. Kurman ◽  
Z. I. Kuvaeva ◽  
...  
Keyword(s):  
Formic Acid ◽  
Hydrogen Chloride ◽  
Carboxylic Acids ◽  
Ethyl Ester ◽  
Ammonia Solution ◽  
Dioxane Solution ◽  
Mixed Anhydride ◽  
Derivatives Of ◽  
Acyl Derivatives ◽  
Methanolic Ammonia

Tert-butyloxycarbonylprolylleucylglycinamide is obtained both by the interaction of tert-butyloxycarbonylprol ylleucylglycine ethyl ester with a methanolic ammonia solution and by the reaction of glycine amide with a mixed anhydride which was synthesized from tert-butyloxycarbonylprolylleucine and isobutylchloroformate. The removal of the tert-butyloxycarbonyl group by the action of formic acid or a dioxane solution of hydrogen chloride and treatment of the resulting salts with the corresponding base yielded a prolylleucylglycinamide, by the interaction of which with acetic, benzoic or 5-phenylisoxazole-3-carboxylic acids chlorides acyl derivatives of prolylleucylglycinamide are obtained.

The role of secondary alcoholic groups of D-galacturonan in its degradation with exo-D-galacturonanase

1980 ◽  
Vol 45 (2) ◽  
pp. 427-434 ◽  
Author(s):  
Kveta Heinrichová ◽  
Rudolf Kohn
Keyword(s):  
Acetyl Derivative ◽  
Competitive Inhibitor ◽  
Hydroxyl Groups ◽  
Pectic Acid ◽  
Substrate Complex ◽  
Enzyme Substrate ◽  
The Individual ◽  
Degradation Degree ◽  
Derivatives Of

The effect of exo-D-galacturonanase from carrot on O-acetyl derivatives of pectic acid of variousacetylation degree was studied. Substitution of hydroxyl groups at C(2) and C(3) of D-galactopyranuronic acid units influences the initial rate of degradation, degree of degradation and its maximum rate, the differences being found also in the time of limit degradations of the individual O-acetyl derivatives. Value of the apparent Michaelis constant increases with increase of substitution and value of Vmax changes. O-Acetyl derivatives act as a competitive inhibitor of degradation of D-galacturonan. The extent of the inhibition effect depends on the degree of substitution. The only product of enzymic reaction is D-galactopyranuronic acid, what indicates that no degradation of the terminal substituted unit of O-acetyl derivative of pectic acid takes place. Substitution of hydroxyl groups influences the affinity of the enzyme towards the modified substrate. The results let us presume that hydroxyl groups at C(2) and C(3) of galacturonic unit of pectic acid are essential for formation of the enzyme-substrate complex.

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