Hydrolytic products of 4-aryl-2,3-dicyano-1-naphthol derivatives

1981 ◽  
Vol 46 (9) ◽  
pp. 2207-2216 ◽  
Author(s):  
Jiří Křepelka ◽  
Iva Vančurová ◽  
Jiří Holubek ◽  
Jiří Roubík
Keyword(s):  
Dicarboxylic Acids ◽  
Ring Closure ◽  
Partial Hydrolysis ◽  
H Nmr ◽  
Antiviral Effects ◽  
Hydrolysis Of ◽  
Derivatives Of ◽  
Naphthol Derivatives ◽  
Intramolecular Ring

Depending on the conditions of hydrolysis, vicinal aromatic dicyano derivatives Ia-Ic gave anhydrides IIa-IIe and imides of 4-aryl-1-alkoxynaphthalene-2,3-dicarboxylic acids, IIIa,b, along with products of partial hydrolysis, decarboxylation and demethylation, IVa-IVd, IVf-IVg, and derivatives of benzo(c)fluorene, Va-Vc. The derivatives Va-Vc were also obtained by acid hydrolysis of dicyano derivatives Id-Ig. Methanolysis of the anhydride IId gave a mixture of positional isomers, IVh, which was esterified to the diester IVe. Intramolecular ring closure of the isomers IVh afforded derivatives of benzo(c)fluorene, VIa-VIb. The structures of the selected compounds were corroborated by IR and 1H NMR spectra. The compounds Va-Vc exhibited antiviral effects and interferonogenic activities in vivo.

scholarly journals Synthesis, Oral Bioavailability and in vivo Activity of Acetal Derivatives of the Selective Antiherpesvirus Agent 9-(3-hydroxypropoxy) Guanine (BRL 44385)

1994 ◽  
Vol 5 (3) ◽  
pp. 147-154
Author(s):  
M. R. Harnden ◽  
R. J. Ashton ◽  
M. R. Boyd ◽  
L. J. Jennings ◽  
D. Sutton ◽  
...  
Keyword(s):  
Oral Administration ◽  
Oral Bioavailability ◽  
Oral Delivery ◽  
Ring Closure ◽  
Guanine Derivatives ◽  
Derivatives Of ◽  
Lesion Severity ◽  
Hsv 1

Acyclic acetal derivatives of the selective antiherpesvirus agent 9-(3-hydroxypropoxy) guanine (BRL44385) and of its 2-aminopurine congener (BRL46720) have been prepared and evaluated in mice for oral delivery of BRL 44385. Guanine derivatives (6 a-c) were prepared via Mitsunobu condensation of an alcohol with a 9-hydroxy-6-methoxypurine (Harnden and Wyatt, 1990). Synthesis of derivatives of 2-aminopurine (10 a-d) was achieved by hydrogenolysis of 9-alkoxy-6-chloropurines, which were obtained either by reaction of an alkoxyamine with 4,6-dichloro-2,5-diformamidopyrimidine and subsequent ring closure or by Mitsunobu condensation of an alcohol with a 6-chloro-9-hydroxypurine. Following oral administration, 2-amino-9-[3-(iso-propoxymethyl)propoxy]-purine (10b, BRL 55792) was very well absorbed and provided high and prolonged concentrations of BRL44385 in the blood. In a cutaneous HSV-1 infection in the ear pinna of mice, orally dosed BRL 55792 was at least 3-fold more potent than both BRL44385 and Acyclovir in reduction of lesion severity.

O-Benzylidene Derivatives of D-Arabinose Diethyl and Dipropyl Dithioacetal

1996 ◽  
Vol 49 (3) ◽  
pp. 273 ◽  
Author(s):  
J Kuszmann ◽  
E Gacsbaitz
Keyword(s):  
Hydrochloric Acid ◽  
Zinc Chloride ◽  
Partial Hydrolysis ◽  
Kinetic Control ◽  
Toluenesulfonic Acid ◽  
Thermodynamic Phase ◽  
Hydrolysis Of ◽  
Derivatives Of

Benzylidenation of D-arabinose diethyl and dipropyl dithioacetals with α,α-dimethoxytoluene in the presence of p-toluenesulfonic acid has been studied in detail. Under kinetic control the two terminal dioxolan -type 4,5-O-(R)- and 4,5-O-(S)-benzylidene diastereomers are formed first which are in equilibrium with each other In the thermodynamic phase of the reaction the corresponding dioxan -type 3,5-O-(R)- benzylidene isomer is formed too, but all three monobenzylidene isomers are gradually converted into the four possible dioxolan -type 2,3 : 4,5-di-O benzylidene diastereomers . The dioxan -type 2,4:3,5-di-O-benzylidene isomer was present only in trace amounts. When benzaldehyde was used as reagent in the presence of hydrochloric acid or zinc chloride only the 2,3: 4,5-di-O-benzylidene diastereomers were formed. Partial hydrolysis of the dibenzylidene derivatives yielded the corresponding 2,3-O-benzylidene diastereomers. Structures, including the chirality of the benzylidene groups, were determined by n.m.r. spectroscopy. A mechanism suggested for the reaction was partially supported by equilibration studies.

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.

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.

scholarly journals Reaktion des Orthovanadinsäure-tri-tert-butylesters mit Monocarbonsäuren / Reaction of Tris-tert-butylorthovanadate with Monocarboxylic Acids

1979 ◽  
Vol 34 (2) ◽  
pp. 163-171 ◽  
Author(s):  
Fritz Preuss ◽  
Joachim Woitschach
Keyword(s):  
Reaction Mechanism ◽  
Nmr Spectroscopy ◽  
Chemical Reactions ◽  
Carboxyl Groups ◽  
Partial Hydrolysis ◽  
Bidentate Ligands ◽  
Monocarboxylic Acids ◽  
H Nmr ◽  
Hydrolysis Of

Abstract Tris-tert-butylorthovanadate VO(OC4H9)3 undergoes reaction with monocarboxylic acids to yield monomeric VO(OC4H9)(RCOO)2; no VO(OC4H9)2(RCOO) or VO(RCOO)3 could be isolated from the reaction mixture. Polymeric dioxovanadium(V)-monocarbox-ylates(VO2RCOO)n are formed by thermolysis or partial hydrolysis of VO(OC4H9)(RCOO)2; the reaction mechanism is studied and discussed. Syntheses of Ba[VO2(CH3COO)3], Ba[VO2(C2H5COO)3] and N(C4H9)4[V4O8Br(CH3COO)4] are described. All compounds obtained are characterized by IR and 1H NMR spectroscopy as well as by chemical reactions. The carboxyl groups are mostly acting as bidentate ligands.

scholarly journals Studies of lipid A fractions from the lipopolysaccharides of Pseudomonas aeruginosa and Pseudomonas alcaligenes

1973 ◽  
Vol 133 (3) ◽  
pp. 563-572 ◽  
Author(s):  
David T. Drewry ◽  
James A. Lomax ◽  
George W. Gray ◽  
Stephen G. Wilkinson
Keyword(s):  
Pseudomonas Aeruginosa ◽  
Lipid A ◽  
Gel Filtration ◽  
Structural Features ◽  
Partial Hydrolysis ◽  
Hexadecanoic Acid ◽  
Alkaline Methanolysis ◽  
Pseudomonas Alcaligenes ◽  
Hydrolysis Of ◽  
Derivatives Of

Lipid A fractions from Pseudomonas aeruginosa and Pseudomonas alcaligenes have similar compositions and structural features. By means of hydrazinolysis of the parent lipopolysaccharides and partial hydrolysis of the deacylation products, it was established that both lipids are derived from the β-(1→6)-linked disaccharide of glucosamine. Phosphorylated derivatives of the disaccharide from Ps. aeruginosa were also characterized. The lipids differ mainly in the absence of hexadecanoic acid and 2-hydroxydodecanoic acid from the lipid from Ps. alcaligenes. Evidence that in Ps. aeruginosa these acids are ester-linked to residues of 3-hydroxyalkanoic acids (including 3-hydroxydecanoic acid) was obtained. Heterogeneity of lipid A fractions was indicated by t.l.c., and by gel filtration of de-O-acylation products from mild alkaline methanolysis of the lipids.

scholarly journals Metabolism of the diacetyl derivatives of stereoisomeric monoacyl-sn-glycerols by rat adipocytes in vitro

1986 ◽  
Vol 235 (3) ◽  
pp. 833-838 ◽  
Author(s):  
W W Christie ◽  
M L Hunter
Keyword(s):  
Oleic Acid ◽  
Significant Degree ◽  
Partial Hydrolysis ◽  
Unesterified Fatty Acid ◽  
Triacylglycerol Biosynthesis ◽  
Bonded Phase ◽  
High Degree ◽  
Hydrolysis Of ◽  
Derivatives Of

Diacetyl long-chain 1(3)- and 2-acyl-sn-glycerols containing either [9,10-3H]oleic acid or [1-14C]palmitic acid were synthesized by partial hydrolysis of the corresponding labelled triacylglycerols and acetylation. They were obtained in a high degree of stereochemical purity by preparative h.p.l.c. on a column containing a diol bonded phase. Each compound was rapidly metabolized by adipocyte preparations in vitro, and a high proportion of the label was recovered in the unesterified fatty acid and triacylglycerol fractions. Negligible amounts of intermediate products of hydrolysis were detected. Triacylglycerols were formed from [9,10-3H]oleic acid and from diacetyl-1(3)-[9,10-3H]oleoyl glycerol precursors at about the same rate, but the 2-isomer was metabolized rather more slowly. The results were consistent with the hypothesis that essentially complete hydrolysis occurred in the medium or at the plasma membrane, through the actions of lipoprotein lipase and monoacylglycerol lipase, and that subsequent esterification took place within the cell. To confirm that no putative intermediate monoacylglycerols were utilized for triacylglycerol biosynthesis via the monacylglycerol pathway, the positional distributions of fatty acids in triacylglycerols from each substrate were determined. No positional selectivity was observed. It was concluded that monoacylglycerols, of an origin exogenous to the tissue, e.g. those derived from plasma triacylglycerols, were not utilized to a significant degree for triacylglycerol biosynthesis in adipose tissue. The diacetyl derivatives of monoacylglycerols may serve as useful stereochemical probes in studies of triacylglycerol biosynthesis via the monoacylglycerol pathway in other tissues.

Reaktionswege zu 3-Acyl-2-oxo-cholest-5-enen / Reaction Ways to 3-Acyl-2-oxo-cholest-5-enes

1981 ◽  
Vol 36 (12) ◽  
pp. 1607-1611 ◽  
Author(s):  
Hans Berbalk ◽  
Karl Eichinger ◽  
Günter Heisler ◽  
Rupert Bauer
Keyword(s):  
Double Bond ◽  
Model Compound ◽  
Total Yield ◽  
Uv Spectra ◽  
H Nmr ◽  
Crude Mixture ◽  
Hydrolysis Of ◽  
Derivatives Of

Two reaction ways to 3-phenylacetyl-2-oxo-cholest-5-ene (10) as model compound for similar A-ring derivatives of steroids are investigated. The first way starts from the known 6,6-ethylenedioxy-3-oxo-5α-cholestane (1) which is reacted with phenylethinyl-magnesiumbromide to the mixture of epimeric alkinols. The crude mixture of epimers is dehydrated to 6,6-ethylenedioxy-3-phenylethinyl-5α-cholest-2-ene (2), which gives after epoxidation of the double bond and reaction of the resulting crude epoxide with 95 proz. HCOOH the fully enolic 2,6-dioxo-3-phenylacetyl-5α-cholestane (3). Because of a very low total yield of this approach to 10 this way is not further investigated. A successful reaction way starts from the known 6β-hydroxy-5α-cholestane-3-one (4). 4 is reacted with phenylethinylmagnesiumbromide, the 6β-OH group is benzoylated and the tert. alkinols dehydrated in successive steps without isolation of the non crystalline intermediate pro­ducts to 6β-benzoyloxy-3-phenylethinyl-5α-cholest-2-ene (6). Hydrolysis of 6 yields 6β-hydroxy-3-phenylethinyl-5α-cholest-2-ene (7) which is epoxidated at the double bond and the crude epoxide reacted with 95 proz. HCOOH to 6β-formyloxy-3-phenylacetyl-5α-cholestan-2-one (8). Hydrolysis of the formylgroup in 8 yields 9, which gives by acid cata­lysed dehydratisation the desired model compound 10. The structure of 10 is confirmed by its 1H NMR and UV spectra.

Syntheses of some N-carboxymethyl derivatives of 4,9-dihydro-3-methyl-4-oxo-1H-(2H)-pyrazolo[3,4-b]quinoline with antiviral effects

1985 ◽  
Vol 50 (9) ◽  
pp. 2010-2014 ◽  
Author(s):  
Stanislav Rádl ◽  
Viktor Zikán ◽  
František Šmejkal
Keyword(s):  
Encephalomyocarditis Virus ◽  
Antiviral Effects ◽  
Derivatives Of

The paper describes the syntheses of 4,9-dihydro-9-carboxymethyl-1,3-dimethyl-4-oxo-1H-pyrazolo[3,4-b]quinoline (Ic), 4,9-dihydro-9-carboxymethyl-2,3-dimethyl-4-oxo-2H-pyrazolo[3,4-b]quinoline (IIc), 4,9-dihydro-1-carboxymethyl-3-methyl-4-oxo-1H-pyrazolo[3,4-b]quinoline (Id), 4,9-dihydro-1-carboxymethyl-3,9-dimethyl-4-oxo-1H-pyrazolo[3,4-b]quinoline (If) and 4,9-dihydro-2-carboxymethyl-3,9-dimethyl-4-oxo-2H-pyrazolo[3,4-b]quinoline (IIf). The compounds were tested in vivo in mice for their efficacy against the virus A2-Hongkong and the encephalomyocarditis virus.

Antiandrogenic A-homo-B,19-dinor-analogues of androgens from 6β-chloro-5-methyl-19-nor-5β-androst-9-enes

1989 ◽  
Vol 54 (5) ◽  
pp. 1318-1326 ◽  
Author(s):  
Alexander Kasal
Keyword(s):  
Partial Hydrolysis ◽  
Lithium Aluminium Hydride ◽  
Lithium Aluminium ◽  
Selective Acylation ◽  
Chloro Derivatives ◽  
Hydrolysis Of ◽  
Derivatives Of ◽  
Antiandrogenic Activity

6β-Chloro derivatives of 5-methyl-19-nor-5β-androst-9-enes (Westphalen diol type) with oxygen functionalities in positions 3 and 17 were converted into diene VI by treatment with lithium aluminium hydride. The lipophilic product of hydrogenation of VI was shown to be 4aα-methyl-A-homo-B,19-dinor-5β,10α-androstane-3β,17β-diol (IX). Various paths leading to dihydrotestosteron analogues, e.g. selective acylation or oxidation of diol IX and partial hydrolysis of diacetate X, have been realized. 17β-Hydroxy-4aα-methyl-A-homo-B,19-dinor-5β,10α-androstan-3-one (XVI) has been found to exhibit antiandrogenic activity.

Sign in / Sign up

Export Citation Format

Share Document