α-Acetylenic ethyleneimides and their reactions with amines

The reaction of aziridines with phenyl and p-chlorophenylpropiolyl chlorides at —30 to 60°C leads only to 1,2-addition products, viz., -acetylenic ethyleneimides, or their isoraerization products, viz., 2-ethynyl-substituted 2-oxazolines. Reactions with amines showed that the p-chlorophenylpropiolic acid ethyleneimides obtained are mild N-acylating agents.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1064–1067, August, 1980.     

Synthesis of 2-oxooxazolo[5,4-b]pyridines and their reactions with amines

Riga Technical University, Riga, LV-1658. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 271–272, February, 1995. Original article submitted December 29, 1994.     

Pyridoxal reactions with amines and aliphatic diamines

Interaction of pyridoxal (3-hydroxy-5-hydroxymethyl-2-methylisonicotinaldehyde) with amines, mono- and disubstituted diamines led to the formation of compounds having in their structure imine, imidazolidine, and pyrimidine moieties. Structure of the obtained compounds was proved by IR data, ¹H NMR spectroscopy, mass spectrometry, and X-ray diffraction analysis.     

Exchange reactions of copper complexes with amines

Square planar mixed ligand complexes of the type [CuLL′] where L = 5-chlorosalicylaldehyde and L′ = acetoacetanilide, have been synthesized on treatment with ammonia. Amine exchange of the above Schiff base complexes has been carried out on treatment with different amines. The reaction with ethanol amine is quite interesting compared to other amines. It reacts with 5-chlorosalicylaldehyde to form a Schiff base, while the β-diketone part is removed in the complex formation. All the complexes were characterized by elemental analysis, spectral studies, magnetic measurement, TLC, and conductane.     

Synthesis of methyl 2-aryl-5-chlorosulfonyl-1,3-oxazole-4-carboxylates and their reactions with amines and amidines

Previously unknown methyl 2-aryl-5-chlorosulfonyl-1,3-oxazole-4-carboxylates have been synthesized. Their reactions with amines and amidines have yielded the corresponding sulfonamides and 6H,7H-[1,3]oxazolo-[5,4-d]pyrimidin-7-ones.     

Fluorinated 2-benzoylcyclohexane-1,3-diones and their vinylogous acyl chlorides in the reactions with primary and secondary amines

The reaction of 5,5-dimethyl-2-[(3-fluoro- and 4-fluoro)benzoyl]cyclohexane-1,3-diones with primary and secondary amines affords their exocyclic enamine derivatives. Under similar conditions 5,5-dimethyl-2-(2-fluorobenzoyl)]cyclohexane-1,3-dione undergoes dehydrofluorination and intramolecular cyclization to give 3,3-dimethyl-2,3,4,9-tetrahydro-1H-xanthene-1,9-dione. The reaction of vinylogous substitution of the enol derivatives of the fluorinated 5,5-dimethyl-2-benzoylcyclohexane-1,3-diones (vinylogous acyl chlorides) with amines results in the formation of the endocyclic enaminoderivatives.     

Lactonization of epoxyendic anhydride in reactions with amines

Reactions of exo-5,6-epoxybicyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicarboxylic anhydride (epoxyendic anhydride) with acyclic, aromatic, heteroaromatic, and nonaromatic heterocyclic amines afforded the corresponding heterocyclization products, substituted exo-2-hydroxy-5-oxo-4-oxatricyclo[4.2.1.0^3,7]nonane-endo-9-carboxamides (oxabrendanes), whose structure was confirmed by the IR and ¹H and ¹³C NMR (including two-dimensional) spectra. Other approaches to the tricyclic compounds were also examined, in particular via reactions of organic peroxy acids with amido acids obtained by aminolysis of endic anhydride.     

Electron-transfer reactions of amines with α-ferrocenylcarbonium ions

The production observed in the reactions of α-ferrocenylcarbonium ions with tertiary amines do not originate from ferrocenylcarbene intermediates. Evidence is presented in support of an electron-transfer mechanism leading to α-ferrocenylcarbinyl radicals as reaction intermediates.     

Reaction of dichloronitrobenzofuroxanes with amines and their derivatives

Reactions of 4,6-dichloro-5,7-dinitrobenzofuroxane and 4,6-dichloro-5-nitrobenzofuroxane with some aliphatic amines were studied. In the reaction of 4,6-dichloro-5,7-dinitrobenzofuroxane with 2,2-dimetoxyethylmethylamine the monosubstituted product was formed for the first time. In the reactions of 4,6-dichloro-5-nitrobenzofuroxane with amines substitution only of one chlorine atom takes place.     

Phosphorus-containing trifluoromethylureas and their reaction with secondary amines

Conclusions O,O-Dialkyl-1-(3-dialkylaminofluoromethyleneureido)-1-methylalkylphosphonates were synthesized by the reaction of O,O-dialkyl-1-(3-trifluoromethylureido)-1-methylalkylphosphonates, obtained from the corresponding carbodiimides, with secondary amines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2618–2620, November, 1988.     

2-Substituted hexahydroacylanthranils: Synthesis and selective reactions with amines

Summary In contrast to their aromatic analogues, the corresponding saturated diamides5–9 are formed exclusively when hexahydro-3,1,4-benzoxazinones (3,4) are reacted with amines. The cyclodehydration reaction of the diamides5–9 cannot be carried out at arbitrarily high temperatures.Saturated Heterocycles, Part 217. Part 216: L. Simon, S. G. Talpas, F. Fülöp, G. Bernáth, G. Argay, A. Kálmán, P. Sohár (1995) J Heterocyclic Chem32: 161     

Novel Petasis boronic acid-Mannich reactions with tertiary aromatic amines

Tertiary aromatic amines can serve as amine substrates for the Petasis boronic acid-Mannich reaction, providing a practical synthetic route for the CC bond formation of α-(4-N,N-dialkylamino-2-alkyloxyphenyl)carboxylic acids. The scope and limitations of this method have been examined.     

Manganese-catalyzed cross-coupling reactions of aliphatic amines with aryl halides

An efficient and convenient protocol has been developed for the N-arylation of aliphatic amines with differently substituted aryl halides using a MnCl₂·4H₂O/l-proline catalyst and NaOt-Bu as the base in DMSO.     

Some reactions of 4H-pyrylium salts with tributylphosphine and with tertiary amines

The phosphonium salt from tributylphosphine and 2,6-di(4-methoxyphenyl)pyrylium perchlorate (3) reacted with diisopropylethylamine in acetonitrile to give 2,2′,6,6′-tetra(4-methoxyphenyl)-Δ^4.4′-bi-4H-pyran in quantitative yield. The reaction of 3 and other 4H-pyrylium salts with tertiary amines gave 4H-pyrans.     

Orientation and mechanism of reactions of aromatic amines with sulfur monochloride

The reaction of m-substituted anilines with sulfur monochloride has been studied. It has been shown that cyclization with the formation of 1, 3, 2-benzothiazathiolium compounds takes place in the position para to the substituent. The introduction of methoxy groups into o-nitroanilines interferes with the displacement of the nitro group by the chlorine atom. A nucleophilic reaction mechanism has been proposed according to which the nitro group is displaced after the formation of the thiathioniaazine ring.     

Competitive reactions of coordinated carbon monoxide and methyl isocyanide with amines

The relative reactivities of CO and CNR ligands with CH₃NH₂ were investigated in complexes which contained both ligands. Like (C₅H₅Fe(CO)₃⁺; the (C₅H₅)Fe(CO)₂(CNCH₃)⁺ complex reacts with CH₃NH₂ to give the carbamoyl complex (C₅)Fe(CO)(CNCH₃)(CONHCH₃); this is a readily reversible reaction. In contrast, (C₅H₅)Fe(CO)(CNCH₃)₂⁺ reacts with CH₃NH₂ to give the amidinium or carbene complex, (C₅H₅)Fe(CO)(CNCH₃)[C(NHCH₃)₂]⁺]. In a slow reaction, (C₅H₅)Fe(PPh₃)(CO)(CNCH₃)⁺ forms the amidinium complex, (C₅H₅)Fe(PPh₃)(CO)[C(NHCH₃)₂]⁺. Factors that affect the site of CH₃NH₂ reaction are discussed. The complexes have been characterized by IR and NMR spectroscopy; a variable temperature NMR study of (C₅H₅)Fe(CO)(CNCH₃)[C(NHCH₃)₂]⁺ indicates restricted rotation around the CN bonds of the amidinium ligand.     

2-Aminobenzimidazole in three-component cyclization reactions with formaldehyde and primary amines

Three-component condensation of 2-aminobenzimidazole and its N-substituted derivatives with formaldehyde and primary amines gave 1,2,3,4-tetrahydro[1,3,5]triazino[1,2-a]benzimidazoles. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 355–356, February, 2007.