N-benzoyl Derivatives Research Articles

Reaction of a histidyl residue analog with hydrogen peroxide in the presence of copper(II) ion

Site-specific damage to a specific amino acid residue of a protein by Cu{sup 2+}/H{sub 2}O{sub 2} was investigated. Observation of specific damage to the histidine residue of the protein was fully supported by a model experiment using N-benzoylhistidine. The reaction of H{sub 2}O{sub 2} toward the substrate was characteristic of a Cu{sup 2+}-catalyzed system and was significantly influenced by pH. Other peroxides and peracids were slightly reactive to the substrate even in the presence of Cu{sup 2+}. Under simulated physiological conditions (pH 7.2, room temperature), incubation with Cu{sup 2+}/H{sub 2}O{sub 2} (0.5 mM CuSO{sub 4}, 50 mM H{sub 2}O{sub 2}) resulted in complete destruction of the substrate within 1 h. Four products including N-benzoyl derivatives of asparagine, aspartic acid, aspartylurea, and formylasparagine were detected as the ring-ruptured products, and three products including 5-(2-benzamidovinyl)imidazole, benzamide, and benzoate were detected as the oxidation products at the {alpha}- and {beta}-positions of the substrate. Plausible mechanisms for oxidation of histidine are proposed.

Stereoselective cycloadditions of acyl-nitroso compounds; an approach to carbapenem synthesis

The adduct obtained from cyclopentadiene and benzohydroxamic acid under oxidising conditions has been used in a stereoselective synthesis of the N-benzoyl derivative of a known intermediate for carbapenem synthesis.

Stereochemistry of nitrogen heterocycles. 68. Stereochemistry of 2,5-dimethyl-4-piperidone, 2,5-dimethyl-4-piperidol, and their N-benzoyl derivatives

The isomers of 1-benzoyl-2,5-dimethyl-4-piperidone were obtained and equilibrated (89.8% cis ⇄ 10.2% trans isomer, preferred conformations 2a, 5e, and 2a, 5a). The position of the equilibrium between the isomers of 2,5-dimethyl-4-piperidone was determined by two independent methods (89.5% trans ⇄ 10.5% cis isomer). The differences in the free energies of the isomers, the conformational energy of the Β-CH3 group, and the energy of syn-axial 1,3-interaction between the CH and the unshared electron pair were calculated; the decrease in the conformational energy of the Β-methyl group in the series of piperidine (1.6), 4-piperidone (1.47), and N-acyl-4-piperidone (1.28 kcal/mole) was explained by the successive weakening of the repulsive interaction between the Β-CH3 group and the n-pair of the nitrogen as a result of the flattening of the ring and of the conjugation between the free electron pair of the nitrogen and the π electrons of the acyl carbonyl group. The last previously unknown fourth isomer of 2,5-dimethyl-4-piperidol, which exists in the 2e,4a,5a conformation, was obtained by the reduction of cis-1-benzoyl-2,5-dimethyl-4-piperidone followed by debenzoylation. In contrast to the secondary amine, its N-benzoyl- and N-benzyl-substituted derivatives exist in the alternative 2a,4e,5e conformation. The configurations and conformations of the isomers were determined by means of the IR and NMR spectra.

Lead tetra-acetate oxidation of tetrahydrobenzazepine enamides: the synthesis of N-acyl substituted tetrahydro-3-benzazocin-2(1H)-ones. A chemical and crystallographic study

Oxidation with lead tetra-acetate of various N-acetyl, N-benzoyl and N-alkoxycarbonyl enamides derived from dihydrobenzazepines leads to a convenient synthesis of N-acyltetrahydrobenzazocinones. Unexpected rate decreases were observed for the N-acetyl and N-benzoyl derivatives with 7,8,9-trimethoxy substitution. Based on crystallographic analysis, these are attributed to conformational effects determining the extent of double bond conjugation with the aromatic ring and, primarily, the nitrogen lone pair. A comparison of oxidation and subsequent cleavage of the various N-alkoxycarbonyltetra-hydrobenzazocinones demonstrated that the N-t-butoxycarbonyl group gives the highest overall yield of the tetrahydrobenzazocinone from the dihydrobenzazepine.

Biosynthesis of Antibiotics of the Virginiamycin Family, 6. Biosynthesis of Virginiamycin S1

The biosynthesis of virginiamycin S 1 has been investigated by means of radiotracer techniques. As a part of this study, a new synthesis of (R,S)-4-oxopipecolic acid was devised, and a procedure for preparation and hplc analysis of amino acid N-benzoyl derivatives was developed. The antibiotic is shown to arise from the amino acids phenylalanine, threonine, methionine, lysine, and proline

Aminolysis of N-Acyl Derivatives of Bicyclic Oxalactams

The aminolysis of N-acyllactams with n-butylamine was carried out in N,N-dimethylformamide at 25°C. The amine reacted with both of exo- and endocyclic carbonyl groups in the N-benzoyl derivatives of bicyclic oxalactams, such as 8-oxa-6-azabicyclo[3.2.1]octan-7-one (1) and the 4(e)-bromo-substituted analogue. In contrast, only the exocyclic carbonyl group in the monocyclic N-benzoyllactams, N-benzoyl-2-pyrrolidone and N-benzoyl-ε-caprolactam, reacted under the same conditions. These results reflect high reactivity of the bicyclic oxalactams in the base-catalyzed ring-opening polymerization. The present aminolysis was kinetically analyzed in order to estimate the reactivity of N-acyllactams more quantitatively.

Diels–Alder reactions of methyl-N-acyl-α,β-dehydroalaninates with cyclopentadiene

A study has been made of the Diels–Alder reaction of methyl-N-acetyl (and benzoyl)-α,β-dehydroalaninates with cyclopentadiene. In the reaction of methyl-N-acetyl-α,β-dehydroalaninate total conversion is obtained under several conditions, while the N-benzoyl derivative shows a lower reactivity. The stereoselectivity of the reaction is determined by 1H nuclear magnetic resonance spectroscopy. Perturbation MO calculations, using wave functions generated by the MNDO method, are used to rationalize the relative reactivity of the dienophiles and the stereoselectivity observed.

An efficient resolution of 3-trifluoromethyl-γ-butyrolactone and its conversion to 5,5,5-trifluoroleucinol

3-Trifluoromethyl-γ-butyrolactone( 2 ) was effectively resolved via its diastereomeric amide( 3 ). 5,5,5-Trifluoroleucinol hydrochloride( 8 ) were prepared in enatiomerically pure form and the absolute configurations were determined by CD spectra of dibenzoyl derivatives ( 9 ) and X-ray analysis of the N-benzoyl derivative ( 11 ).

Structure and synthesis of physoperuvine: x-ray crystal and molecular structures of the n-benzoyl derivatives of (±)-3- and (+)-4-methylaminocycloheptanone

Single-crystal X-ray analyses have defined the structures and solid-state conformations of (±)- N-benzoyl-3-methylaminocycloheptanone [(±)- 3 ]and (+)- N-benzoyl-4-methylaminocycloheptanone [(±) 4 ]. Resolution of (±)-[4- methylaminocycloheptanone α 1-hydroxytropane]to yield the (+)-enantiomer. Identical in all respects with the free base from natural (+)-physoperuvine, was achieved via the di-p-toluoyl-(+)-tartrate salt.

Cyclic meso-ionic compounds. Part 23. Novel chemistry of 1,2,4-thiadiazoles and their transformation into meso-ionic 1,2,4-thiadiazolium derivatives

Representatives of two new classes of meso-ionic heterocycles have been synthesised, the 1,2,4-thiadi-azolium-3-olate (8) and the 1,2,4-thiadiazolium-3-tosylaminide(25). The reactions of 1,2,4-thiadiazoles and nucleophiles follow two general pathways: (i) reductive transformation to N-thiobenzoyl derivatives and (ii) elimination of elemental sulphur and the formation of N-benzoyl derivatives. A mechanistic rationale is proposed for the operation of pathways (i) and (ii). Earlier views on the oxidative formation of certain 1,2,4-thiadiazoles are corrected. A novel synthetic route to heterocycles containing sulphur–nitrogen bonds is described. 1,2,4-Thiadiazoles are formed by oxidation of N-thiobenzoylureas and N-thiobenzoylguanidines by bis(4-methoxyphenyl) telluroxide.

ChemInform Abstract: STRUCTURE‐ACTIVITY RELATIONSHIPS AMONG SUBSTITUTED N‐BENZOYL DERIVATIVES OF PHENYLALANINE AND ITS ANALOGS IN A MICROBIAL ANTITUMOR PRESCREEN. I: DERIVATIVES OF O‐FLUORO‐DL‐PHENYLALANINE

Chemischer InformationsdienstVolume 13, Issue 41 Other Subjects ChemInform Abstract: STRUCTURE-ACTIVITY RELATIONSHIPS AMONG SUBSTITUTED N-BENZOYL DERIVATIVES OF PHENYLALANINE AND ITS ANALOGS IN A MICROBIAL ANTITUMOR PRESCREEN. I: DERIVATIVES OF O-FLUORO-DL-PHENYLALANINE T. T. OTANI, T. T. OTANISearch for more papers by this authorN. R. BRILEY, N. R. BRILEYSearch for more papers by this author T. T. OTANI, T. T. OTANISearch for more papers by this authorN. R. BRILEY, N. R. BRILEYSearch for more papers by this author First published: October 12, 1982 https://doi.org/10.1002/chin.198241357AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume13, Issue41October 12, 1982 RelatedInformation

ChemInform Abstract: STRUCTURE AND CONFORMATION OF N‐BENZOYL DERIVATIVES OF THE BIOLOGICALLY IMPORTANT 3‐AMINO‐2,3,6‐TRIDEOXY‐L‐HEXOSES AND THEIR SYNTHETIC PRECURSOR Γ‐ AND Δ‐LACTONES; A PROTON AND CARBON‐13 NUCLEAR MAGNETIC RESONANCE STUDY

Chemischer InformationsdienstVolume 13, Issue 27 Physical Organic Chemistry ChemInform Abstract: STRUCTURE AND CONFORMATION OF N-BENZOYL DERIVATIVES OF THE BIOLOGICALLY IMPORTANT 3-AMINO-2,3,6-TRIDEOXY-L-HEXOSES AND THEIR SYNTHETIC PRECURSOR Γ- AND Δ-LACTONES; A PROTON AND CARBON-13 NUCLEAR MAGNETIC RESONANCE STUDY G. FRONZA, G. FRONZASearch for more papers by this authorC. FUGANTI, C. FUGANTISearch for more papers by this authorP. GRASSELLI, P. GRASSELLISearch for more papers by this author G. FRONZA, G. FRONZASearch for more papers by this authorC. FUGANTI, C. FUGANTISearch for more papers by this authorP. GRASSELLI, P. GRASSELLISearch for more papers by this author First published: July 6, 1982 https://doi.org/10.1002/chin.198227059AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume13, Issue27July 6, 1982 RelatedInformation

Structure-Activity Relationships Among Substituted N-Benzoyl Derivatives of Phenylalanine and Its Analogs in a Microbial Antitumor Prescreen I: Derivatives of o-Fluoro-DL-phenylalanine

Twelve derivatives of o-fluoro-DL-phenylalanine containing fluorine, chlorine, methoxy, and nitro radicals in various positions of the aromatic ring of the benzoyl group were prepared and tested in a Lactobacillus casei system. It was found that most substitutions in the benzoyl phenyl ring resulted in a compound exhibiting greater growth-inhibiting activity than the nonsubstituted benzoyl-o-fluorophenyl-alanine. The greatest activity was observed in the ortho- substituted fluoro compound and the meta- and para- substituted chloro and nitro compounds. With the methoxy group, the position of substitution appeared unimportant, since all three methoxy isomers exhibited essentially equal inhibition. Nitro substitution in the ortho position had a protective effect in that the product was less active than the unsubstituted ben-zoyl-o -fluoro-DL-phenylalanine.

Structure and conformation of N-benzoyl derivatives of the biologically important 3-amino-2,3,6-trideoxy-L-hexoses and their synthetic precursor γ- and δ-lactones; a1H and13C nuclear magnetic resonance study

The 3-benzoylamino-2,3,6-trideoxy-L-xylo- and L-arabino-hexoses have been shown to exist in the α- and β-pyranose forms, whereas the compounds with the L-ribo- and L-lyxo-configurations exist as mixtures of α- and β-pyranose and α- and β-furanose tautomers. All the pyranoid compounds are stable in the 1C4(L) conformation except the L-xylo-α-derivative, which exists in a conformational equilibrium with about 15% of the 4C1(L) form. The L-ribo-α- and β-furanoses adopt the 1T2(or E2) and 2T1(or 2E) conformation, respectively. The γ-lactones exist in a conformational equilibrium except the L-arabino-γ-lactone, which exists in the 4T3(or E3) conformation. The δ-lactones preferentially adopt the half-chair conformation although some distortions must be invoked for the L-arabino-δ-lactone to account for the observed coupling constants.

Research on unsaturated lactones. 49. Synthesis of thiazolidines that contain an ?,?-unsaturated ?-lactone ring

The corresponding thiazolidines containing a lactone ring and their hydrochlorides and N-benzoyl derivatives were obtained by the reaction of 2-acetyl-3,4,4-trimethyl-2-buten-4-olide with thioglycolic or mercaptosuccinic acids and ammonium carbonate.

The effect of ring size in N-benzoyl saturated heterocyclic amides

The structures of the N-benzoyl derivatives of aziridine, azetidine, pyrrolidine, piperidine, hexamethyleneimine and heptamethyleneimine in solution have been investigated by 13C n.m.r. spectroscopy. In conjunction with literature crystal structure and dynamic intramolecular exchange data, it has been concluded that N-benzoylaziridine and N-benzoylazetidine possess pyrimidal nitrogen atoms in solution. The N-benzoyl derivatives of pyrrolidine, �piperidine, hexamethyleneimine and heptamethyleneimine have planar or near planar nitrogen atoms.

Synthesis of the n-benzoyl derivatives of [formula omitted]- [formula omitted], [formula omitted]- [formula omitted] and [formula omitted]- [formula omitted] ( [formula omitted]-vancosamine) isomers of 2,3,6-trideoxy-3- [formula omitted]-methyl-3-aminohexose from a non-carbohydrate precursor

The synthesis of the N-benzoyl derivatives of L - arabino (10), L - xylo (13) and L - lyxo ( L -vancosamine) (12) 2,3,6-trideoxy-3- C -methyl-3-aminohexose from the (2 S ,3 R ) diol (1) prepared in fermenting bakers' yeast from α-methylcinnamaldehyde and acetaldehyde is reported

N-benzoyl Derivatives of Amino Acids and Amino Acid Analogs as Growth Inhibitors in Microbial Antitumor Screen

Twenty-seven N-benzoyl derivatives of amino acids and amino acid analogs were prepared and tested for growth-inhibitory activity in a microbial antitumor screen. Of these, 19 showed some inhibitory capacity, from a modest 13% to a potent 96% at 1 mg/ml. The activities of the “modest” inhibitors were comparable to those of most inhibitory chloroacetyl and trifluoroacetyl derivatives reported earlier. The intermediate inhibitors were as active as N-chloroacetyl-β-hydroxy-D-norleucine isomer B, the most active acyl derivative noted previously. The most active compounds in this study were N-benzoyl-p-chloro-DL.-phenylalanine and N-benzoyl-m-fluoro-DL-phenylalanine, which inhibited the test organism almost completely under the assay conditions.

Sphingolipid base metabolism. Chemical syntheses and properties of N-acetyl derivatives of 4R-, 4S-S, 5R-, and 5S-hydroxysphinganine

The following compounds were prepared by chemical synthesis from tribenzoylsphingosine: (2S,3S,4S)-2-acetamido-1,3,4-trihydroxyoctadecane, (2S,3S,4R)-2-acetamido-1,3,4-triydroxyoctadecane, (2S,3S,5S)-2-acetamido-1,3,5-trihydroxyoctadecane, and (2S,3S,5R)-2-acetamido-1,3,5-trihydroxyoctadecane. These compounds were characterized by melting point determination, low and high resolution mass spectra, infrared, optical rotation, chromatographic, and chemical degradation studies. In addition, each of the compounds was converted to the corresponding free base and N-benzoyl derivative. (2S,3S,4R)-2-Benzylamino-1,3,4-trihydroxyoctadecane was prepared from the N-benzoyl derivative of authentic phytosphingosine.

N-Benzoyl Derivatives of Amino Acids and Amino Acid Analogs as Inhibitors in Microbial Antitumor Screen

N-Benzoyl Derivatives of Amino Acids and Amino Acid Analogs as Inhibitors in Microbial Antitumor Screen