Alkylation by secondary alcohols. I. The reaction of xanthydrol with some N1-monosubstituted sulfanilamides and related compounds

1967 ◽  
Vol 45 (13) ◽  
pp. 1411-1424 ◽  
Author(s):  
R. E. Moskalyk ◽  
L. G. Chatten
Keyword(s):  
Nitrogen Atom ◽  
Tautomeric Form ◽  
Heterocyclic Ring ◽  
The Other ◽  
Secondary Alcohols ◽  
Amino Group ◽  
Aromatic Character ◽  
Carbonium Ion ◽  
Other Hand ◽  
Related Compounds

Sulfanilamides were found to undergo alkylation with xanthydrol, yielding either mono- or di-xanthenyl derivatives. The site of substitution, common to all sulfanilamides having a free p-amino group, was shown to be the N4-position in the sulfanilamide molecule. Three additional unique reactive sites were observed. Sulfanilamides carrying a thiazole, thiadiazole, or pyridazine substituent in the N1-position were also alkylated on the annular nitrogen atom of the heterocyclic ring, the reaction having occurred from the imido tautomeric form. Sulfisoxazole (IK), on the other hand, reacted from the amido form to give the N1,N4-dixanthenyl derivative. Sulfadimethoxine (Ih) was substituted at carbon, as well as at nitrogen, to yield N4-xanthenyl-N1-(2,6-dimethoxy-5-(9-xanthenyl)-4-pyrimidyl)sulfanilamide.Sulfanilamides possessing pKa values of about 5.5 were found to be sufficiently acidic to catalyze their own reaction with xanthydrol, and no external catalyst was necessary. The exceptional ease of formation of the xanthylium ion was postulated to be associated with the resulting stability of this carbonium ion by virtue of its acquired aromatic character.

Dative behavior of N-heterocyclic carbenes (NHCs) with selenium in Se-NHC compounds

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Munazzah Yaqoob ◽  
Mahvish Abbasi ◽  
Hira Anwar ◽  
Javed Iqbal ◽  
Mohammad Asad ◽  
...  
Keyword(s):  
Nitrogen Atom ◽  
Carbon Atom ◽  
Lone Pair ◽  
Heterocyclic Ring ◽  
Heterocyclic Carbenes ◽  
The Other ◽  
Donor Ligands ◽  
Important Research ◽  
Dative Bond ◽  
Back Bonding

Abstract N-heterocyclic carbenes (NHCs) are an eminent class of carbenes having a heterocyclic ring in which a divalent carbon atom is attached directly to a nitrogen atom. In the NHCs, the donation of lone pair is another important research in the dative bonding and not only in NHCs the dative bond plays a functionalized role in the other classes of complex formation like ylidones L → E ← L and carbones L → C ← L. M–NHC bond is L-M sigma-dative bond and NHCs are considered as strong sigma-donor ligands. The clear picture of the M–NHC bond can be better understood by M–NHC pi-interaction. M-L pi interaction is comprised of two steps. One is L → M sigma-donation and M → L π* back bonding. This dative donor nature of NHC and also its behavior in organoselenium is studied through DFT in which it’s optimized structure, bond lengths, molecular vibrations are calculated.

Embryonic Responses to Structurally Related Inhibitors

Development ◽  
1960 ◽  
Vol 8 (4) ◽  
pp. 445-456
Author(s):  
Kathe Liedke ◽  
H. B. Gillespie ◽  
Samuel Graff
Keyword(s):  
Nitro Group ◽  
Rana Pipiens ◽  
The Other ◽  
Amino Group ◽  
Inhibitory Effects ◽  
Tail Bud ◽  
Cytotoxic Effects ◽  
Other Hand

Substituted benzotriazoles (Bt) have been shown to bring about interesting inhibitory effects on Rana pipiens embryos of 2-cell to tail-bud stages (Liedke, Engelman, & Graff, 1954, 1955, 1957a, 1957b). These benzotriazoles did not have selective cytotoxic effects on sensitive embryonic structures as similarly substituted benzimidazoles (Bz) and quinoxalines (Q) invariably did. The latter compounds, Bz and Q, were most active against younger stages, especially those in cleavage. On the other hand, it was found that the susceptibility to the benzotriazoles increased with age of embryo; more differentiated stages were affected most. The type of response was determined by the parent structure, but certain substituents, the nitro group in particular, appeared to enhance the magnitude of the effect. The activating effect of the nitro group was in turn modified to varying degree by an accompanying methoxy, hydroxy, or amino group.

Mechanism and Stereochemistry of the Hydrolysis of 4-Arylamino-1,2,3,4- tetrahydroquinaldines

1974 ◽  
Vol 52 (6) ◽  
pp. 884-887 ◽  
Author(s):  
T. P. Forrest ◽  
G. A. Dauphinee ◽  
W. F. Miles
Keyword(s):  
Nitrogen Atom ◽  
Equilibrium Mixture ◽  
Hydroxyl Group ◽  
Amino Group ◽  
Heterocyclic Nitrogen ◽  
Carbonium Ion ◽  
Kinetically Controlled ◽  
Leaving Group ◽  
Acid Catalyzed ◽  
Hydrolysis Of

Rates of acid-catalyzed hydrolysis of the benzylic amino group in stereoisomers of 4-arylamino-1,2,3,4-tetrahydroquinaldines have been determined by n.m.r. spectroscopy. Those isomers which have a pseudo-axial leaving group react more rapidly than those with a pseudo-equatorial leaving group, forming in each case the isomer with a pseudo-axial hydroxyl group as the kinetically controlled product. This product is converted in time to an equilibrium mixture of the two stereoisomeric alcohols. The reaction is inhibited by excess acid and appears to proceed through an intermediate carbonium ion which is stabilized by the heterocyclic nitrogen atom.

Preparation and 31P NMR characterization of N-bonded complexes of platinum(II) with a phosphadithiatriazine: X-ray structure of trans-PtCl2(Pet3)(η1-N-Ph2PS2N3)

1992 ◽  
Vol 70 (10) ◽  
pp. 2602-2606 ◽  
Author(s):  
Tristram Chivers ◽  
Robert W. Hilts ◽  
Ian H. Krouse ◽  
A. Wallace Cordes ◽  
Randal Hallford ◽  
...  
Keyword(s):  
Nitrogen Atom ◽  
Free Ligand ◽  
Heterocyclic Ring ◽  
Structural Features ◽  
The Other ◽  
Monoclinic Space Group ◽  
Hydrogen Atoms ◽  
Absorption Bands ◽  
X Ray ◽  
Nmr Characterization

The reaction of Ph2PS2N3 with [Pt2(μ-Cl)2(PEt3)4][BF4]2 or [PtCl2(PEt3)]2, in dichloromethane at 23° C produces the 1:1 adducts cis-[PtCl(PEt3)2(Ph2PS2N3)][BF4], 3, and trans-[PtCl2(PEt3)(Ph2PS3N2)], 4, respectively, in good yields. The 31P NMR data for 3 and 4 indicate that (i) the platinum is attached to a nitrogen atom adjacent to phosphorus in both these adducts, (ii) the PEt3 ligands in 3 are in mutually cis positions, and (iii) the PEt3 ligand in 4 is trans to the heterocyclic nitrogen. These structural features were confirmed by an X-ray analysis of 4. Crystals of 4 are monoclinic, space group P21/c, with a = 14.920(3) Å, b = 8.966(5) Å, c = 19.103(5) Å, β = 109.32(2)°, V = 2411.6(16) Å3, and Z = 4. The least-squares refinement with anisotropic thermal parameters for all non-hydrogen atoms converged at R = 0.050 and Rw = 0.053. The Pt—N bond length is 2.122(15) Å and the coordinated nitrogen atom is lifted ca. 0.63(2) Å out of the plane containing the other heterocyclic ring atoms. The attachment of a platinum(II) centre to the PN3S2 ring perturbs the S—N bond lengths significantly. The S—N distance involving the coordinated nitrogen is 1.672(16) Å, while the other S—N distances are 1.631(19), 1.555(19), and 1.562(19) Å, indicative of a localized sulfur diimide (-N=S=N-) structure. The UV–visible spectra of 3 and 4 in CH2Cl2 exhibit absorption bands at 514 and 528 nm, respectively, but dissociation of these adducts to give the free ligand Ph2PS2N3 occurs readily in dilute solution.

Synthesis of Some Diazepinones, Oxazepinones, Pyrimidoquinazolinones and Related Compounds from 1,4-Bis(ethoxycarbonyl)-2,5-diamino-1,4-cyclohexadiene

1980 ◽  
Vol 35 (11) ◽  
pp. 1395-1397 ◽  
Author(s):  
Fathy A. Amer ◽  
El-Sayed Afsah ◽  
Mohamed A. Metwally ◽  
Mohamed T. El-Zimaity
Keyword(s):  
Polyphosphoric Acid ◽  
The Other ◽  
Spectroscopic Methods ◽  
Other Hand ◽  
Related Compounds

AbstractInteraction of o-phenylenediamine with 1,4-Bis-(ethoxycarbonyl)-2,5-diamino-1,4-cyclo-hexadiene (1) gave 2, which cyclised to the hexahydrobenzodiazepinone (3). On the other hand, interaction of 1 with o-aminophenol, gave compound 4 which on treatment with polyphosphoric acid gave the tetrahydrobis-benzooxazepinone (11). Treatment of 1 with phenylisothiocyanate and formamide afforded the dithiopyrimidoquinazolinone (8) and the tetrahydropyrimidoquinazolinone (9), while the interaction of 1 with benzenesulphonyl-chloride gave dibenzenesulphonamido-cyclohexadiene dicarboxylate (10). The structure of these compounds was established by chemical and spectroscopic methods.

Stereocontrolled catalytic hydrogenations of 3-oxocholestanes and some related compounds to the corresponding axial 3-alcohols

1980 ◽  
Vol 58 (11) ◽  
pp. 1061-1068 ◽  
Author(s):  
Masayoshi Ishige ◽  
Michio Shiota
Keyword(s):  
Carbonyl Group ◽  
Cobalt Catalyst ◽  
Solvent Polarity ◽  
The Other ◽  
Nonpolar Solvents ◽  
Ketone Carbonyl Group ◽  
Other Hand ◽  
Ketone Carbonyl ◽  
Related Compounds ◽  
Alcohol Formation

Catalytic hydrogenations of 5α-cholestan-3-ones and related compounds with Urushibara nickel A catalyst in cyclohexane gave a distinct preponderance of unstable axial 3α-ols. Product ratios of axial alcohols decreased with increasing solvent polarity. For 3-oxo-5α-steroids, the cobalt catalyst was less selective for the axial alcohol formation. On the other hand, conversion of 5β-cholestan-3-one into the corresponding axial 3β-ol was most successfully attained by hydrogenation catalyzed by Urushibara cobalt A catalyst in methanol. For such a 5β-ketone, alcoholic media with higher polarities were more favorable for giving the product rich in axial alcohol. The stereochemistry of the products obtained from hydrogenations conducted in nonpolar solvents may be understood in terms of the steric congestion around the ketone carbonyl group. However, when alcohols were used as solvents, the product ratios obtained did not correlate well with the congestion ratios of substrates.

Fibrinogen-Induced Polymerization Via the Process of Methylation

1979 ◽  
Vol 42 (05) ◽  
pp. 1398-1410
Author(s):  
A J Osbahr
Keyword(s):  
Carboxylic Acid ◽  
Thionyl Chloride ◽  
Acid Group ◽  
Fibrin Clot ◽  
Spectrophotometric Analysis ◽  
The Other ◽  
Amino Group ◽  
Methyl Sulfate ◽  
Carboxylic Acid Groups ◽  
Other Hand

SummaryFibrinogen is polymerized by a number of group specific reagents including diazomethane, thionyl chloride and di-methyl sulfate at pH 7.4. The relationship between the number of methyl groups incorporated into fibrinogen and the extent of polymerization was evaluated. With diazomethane and thionyl chloride as modifying agents, polymerization ensued in approximately IV2 hr with extensive modification of fibrinogen. On the other hand, m�thylation via di-methyl sulfate-induced polymer formation occurs in approximately 35 min with primarily carboxylic acid group esterification. The polymerized fibrinogen formed under these conditions exhibited properties that were closely similar with the physiological fibrin clot.Amino group determinations revealed the m�thylation of amino acid residues other than the expected esterification of carboxylic acid groups. Diazomethane induced both N- methylation of lysine, as well as O-methylation of tyrosine, as estimated from spectrophotometric analysis. On the other hand, thionyl chloride modified only a small number of amino groups, and di-methyl sulfate modification resulted in no significant amounts of amino group methylation during the process of modification induced polymerization of fibrinogen.The profile of the number of methoxyl groups incorporated into fibrinogen with time for diazomethane modification may reflect a conformational change in the protein due to a more nonspecific m�thylation. Both the reagent and the conditions of modification were found to be important in achieving a selective modification of fibrinogen.A possible interpretation of these results is the esterification of carboxylic acid groups in the fibrinogen with reduction in the prevailing carboxylate ion negative repulsion, thereby achieving an increased protein-protein interaction with a resulting polymerization.

Pyrimidine Derivatives and Related Compounds, IX / Preparation of 5-Aminopyrazolo[1,5-a]pyrimidines and of Oxazino[4,5 : 5,6]pyrazolo[1,5-a]pyrimidines, a New Ring System

1977 ◽  
Vol 32 (12) ◽  
pp. 1478-1481 ◽  
Author(s):  
Mohamed Hilmy Elnagdi ◽  
Sherif Mahmoud Fahmy ◽  
Mohamed Riffaat Hamza Elmoghayar ◽  
Abdalla Mohamed Negm
Keyword(s):  
Acetic Acid ◽  
Pyrimidine Derivative ◽  
Ring System ◽  
The Other ◽  
Reaction Products ◽  
Pyrimidine Derivatives ◽  
Other Hand ◽  
Related Compounds

Whereas the 5-aminopyrazole derivatives (1 a, b) react with ethyl β-amino-β-trichloro-methylmethylenecyanoacetate (2) in basic media to yield the corresponding 5-aminopyrazolo[1,5-a]pyrimidine derivatives (3a, b), the reaction of la, b with 2 in refluxing acetic acid has afforded oxazino[4,5:5,6]pyrazolo[1,5-a]pyrimidine derivatives.5-Amino-3-phenyl-4-phenylazopyrazole (12) reacted with 2 in refluxing pyridine to yield the 5-amino-2-phenyl-3-phenylazopyrazolo[1,5-a]pyrimidine derivative (18). On the other hand, the reaction of 12 and 2 in refluxing acetic acid has afforded a mixture of the oxazino[4,5:5′,6′]pyrazolo[1,5-a]pyrimidine derivatives (14) and the pyrazolo[3,4-d]-astriazine derivatives (15). The mechanism of the formation of reaction products is discussed.

Stereochemistry of bimolecular nucleophilic opening of a dioxolenium ring fused to an anchored cyclohexane system

1969 ◽  
Vol 47 (9) ◽  
pp. 1445-1459 ◽  
Author(s):  
J. F. King ◽  
A. D. Allbutt
Keyword(s):  
Transition States ◽  
Heterocyclic Ring ◽  
The Other ◽  
Cyclohexane Ring ◽  
Methyl Group ◽  
Other Hand ◽  
Opening Ratio ◽  
Nucleophilic Reagents

This paper describes the characterization of certain dioxolenium salts in which the heterocyclic ring is fused (via positions-4 and -5) to an anchored cyclohexane ring, and the steric course of their bimolecular cleavage with nucleophilic reagents. It was found that diaxial opening is normally favored strongly over diequatorial; this is accounted for in terms of differences in angle strain in the transition states. The presence of an axial (angular) methyl group gave a preference for diequatorial opening; on the other hand an analogous investigation of the diaxial: diequatorial opening ratio with epoxides showed the stereochemistry of the reaction to be virtually insensitive to an angular methyl group. These observations are interpreted in terms of the different non-bonded interactions arising from the different geometrical arrangements of epoxides and dioxolenium ions. The variation in the diaxial: diequatorial opening ratio is shown to be of significance in the interpretation of rates of diaxial → diequatorial rearrangement.

Synthesis of 2-Acetoacetyl- and 2-OxaIoacetyl-1,3-indandiones and Related Compounds

1988 ◽  
Vol 43 (7) ◽  
pp. 897-900 ◽  
Author(s):  
W. S. Hamama ◽  
M. Hammouda ◽  
E. M. Afsah
Keyword(s):  
Ethyl Acetate ◽  
Mannich Reaction ◽  
Selenium Dioxide ◽  
The Other ◽  
Molar Ratio ◽  
Diethyl Oxalate ◽  
Phenyl Hydrazine ◽  
Claisen Condensation ◽  
Other Hand ◽  
Related Compounds

Abstract Claisen condensation of 2-acetyl-1,3-indandione (1) with ethyl acetate afforded the 2-acetoacetyl-1,3-indandione (2) which upon treatment with benzylamine and paraformaldehyde in a molar ratio of (1:1:2) and (1:2:4) afforded the piperidinone and the diazabicyclic derivative (4) and (5) respectively. On the other hand, Claisen condensation of 1 with diethyl oxalate yielded two products (6) and (9). The behaviour of 6 towards phenyl hydrazine, and of 9 towards selenium dioxide and double Mannich reaction were also investigated.

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