The synthesis of certain 4-mono- and 4,7 dihydroxy-1,10-phenanthrolines

Aminocrotonates and cinnamates formed by the action of ethyl acetoacetate and ethyl benzoylacetate on substituted 8-aminoquinolines have been cyclized to 4-hydroxy and 4,7-dihydroxy-1,10-phenanthrolines.     

Reissert compound studies. XLV. The phenanthridine reissert compound

A series of phenanthridine Reissert compounds and Reissert analogs have been prepared using the trimethylsilyl cyanide method. The reactions of the conjugate base and fluoroborate salt have been studied and found, generally, to be similar to those of the isoquinoline Reissert compounds.     

Reissert compound studies. XVII. Phosphorus-containing reissert compound analogues

The reaction of isoquinoline, potassium cyamide, and chlorophosphates or chlorothiophosphates leads to the formation of phosphorus containing analogues of Reisert compounds. These analogues can be converted by base to an anion which undergoes elimination to isoquinaldonitrile or which can be alkylated. Acid-catalysed hydrolysis of the analogues leads to isoquinoline.     

Reissert compound studies. LXIV. Reissert compound and other products from an isolated N-benzoylisoquinolinium triflate salt

In the presence of trimethylsilyl trifluoromethanesulfonate, a methylene chloride solution of isoquinoline and benzoyl chloride gave N-benzoylisoquinolinium triflate ( 3 ) and N-H-isoquinolinium triflate ( 4 ). Depending on the reaction conditions, reaction of 3 may occur on the isoquinoline ring yielding a Reissert compound and 1,2-dihydroisoquinoline species. Otherwise, reactions transpire on the carbonyl of 3 to give an amide, an ester, and an anhydride.     

Reissert compound studies. XXXIV. Base-catalyzed reactions of the phthalazine reissert compound

The phthalazine Reissert compound has been used to convert phthalazine to 1-benzylphthalazines, bisbenzylphthalazines, 1,4-disubstituted phthalazines, 1-cyanophthalazine, and a number of other phthalazine derivatives including the tricyclic compound 14 .     

Thermal decomposition of metal complexes: II. Mixed complexes of iron(II) iodide with 1,10-phenanthroline,and 4,7-disubstituted-1,10-phenanthrolines

The thermal behavior of the Fe(II) iodide mixed complexes with 1,10-phenanthroline and 4,7-disubstituted phenanthrolines in nitrogen atmosphere is investigated.In order to determine to what extent small changes in ligand field symmetries influence the “activation energy” E_a, this energy is determined. The results are discussed in relation to the changes of the σ and π bonds.     

Reissert compound studies. XL. The first monocyclic reissert compounds

Pyridazine and pyrimidine have been reacted with trimethylsilyl cyanide and benzoyl chloride to give the first examples of Reissert compounds derived from monocyclic systems.     

Reissert compound studies. XLIII. The pyrido[2,3-b]pyrazine reissert compound

Both pyrido[2,3-b]pyrazine (5-azaquinoxaline) and 2,3-dimethyl-5-azaquinoxaline undergo Reissert compound formation across the 5,6-position.     

Reissert compound studies LXVI. Regioselective synthesis of pyridine reissert analogs

The reaction of ethyl chloroformate and pyridine with diethylaluminum cyanide as the cyanide source gave the Reissert analog, 1-ethoxycarbonyl-4-cyano-1,4-dihydropyridine and not the expected 1,2-dihydro regio isomer. Under the same conditions, 3-bromopyridine also directly gave the corresponding 1,4-dihydro Reissert analog. Reinvestigation of trimethylsilylcyanide, as the cyanide source, resulted in the observation that both regio isomers are formed and the ratio of these isomers are affected by both solvent polarity and by copper(I) iodide.     

Reissert compound studies. LXVII. The pyrido[3,4-b]pyrazine reissert compound

The pyrido[3,4-b]pyrazine systems investigated were found to form Reissert compounds in the presence of an acyl halide (or chloroformate) and trimethylsilyl cyanide. Only the mono Reissert compounds were isolated. In the case of 2,3-diphenylpyrido[3,4-b]pyrazine ( 7 ), its reaction with benzene sulfonyl chloride and trimethylsilyl cyanide gave 5-cyano-2,3-diphenylpyrido[3,4-b]pyrazine ( 16 ). Alkylation of the Reissert compound 11 and analog 12 either directly gave the alkylated hetercyclic base or the alkylated Reissert analog compound.     

Synthesis, characterization and ethylene oligomerization studies of nickel complexes bearing 2-imino-1,10-phenanthrolines

A series of nickel (II) complexes ligated by 2-imino-1,10-phenanthrolines were synthesized and characterized by elemental and spectroscopic analysis as well as by single-crystal X-ray crystallography. X-ray crystallographic analysis reveals complexes 3, 5, 7 and 11 as the five-coordinated distorted trigonal-bipyramidal geometry. Upon activation with Et₂AlCl, these complexes exhibited considerably high activity for ethylene oligomerization (up to 3.76 × 10⁷ g mol⁻¹(Ni) h⁻¹ for 12 with 10 equiv. of PPh₃). The ligand environment and reaction conditions significantly affect the catalytic activity of their nickel complexes.     

Synthesis and properties of fluorine-containing heterocyclic compounds. V. Trifluoromethyl-1,8- and 1,10-phenanthrolines

The condensation of ethyl trifluoroacetoacetate with various heterocyclic amines yielded 2-(trifluoromethyl)phenanthrolin-4-ones. The structures of these compounds were established from a study of their infrared and ultraviolet spectra. Substituted phenanthrolines were prepared by nucleophilic attack on a chlorophenanthroline. The oxidation of 5-methoxy-2-trifluoromethyl-1,10-phenanthroline yielded an o-quinone which was treated with typical quinone reagents. A molecular orbital calculation was carried out in an attempt to explain the ease of reduction of the 1,10-phenanthroline system and the colors of the reduced compounds.     

Reissert compound studies. XXX. Synthesis and alkylation of some new reissert compounds

The synthesis of several new isoquinoline Reissert compounds is described. Alkylation reactions of the anions of these new Reissert compounds and a rearrangement reaction are reported.     

Reissert compound studies. XXXV. Acid-catalyzed condensations of the phthalazine reissert compound and condensations of phthalazine reissert compound salt

The phthalazine Reissert compound hydrofluoroborate undergoes condensation with alkynes to give pyrrolo[2,1-α]phthalazines and with alkenes to give 2-(1-phthalazyl)pyrroles. The phthalazine Reissert compound undergoes acid catalyzed condensations with some alkenes but the intermediate is of sufficient stability to be isolated. This same type of intermediate can also be isolated in the acid-catalyzed hydrolysis of the phthalazine Reissert compound.     

Reissert compound studies. XXVII. The reaction of the anion with 4-piperidones

The anion of the isoquinoline Reissert compound has been found to react with 4-piperidones to give esters of tertiary alcohols.     

Reissert compound studies. XXXVII. Attempts to form reissert compounds from quinazoline and cinnoline

Reaction of quinazoline with trimethylsilyl cyanide and benzoyl chloride gave 2,4-dicyano-1,3-dibenzoyl-1,2,3,4-tetrahydroquinazoline as the major product. This compound undergoes monoalkylation with methyl iodide in the presence of sodium hydride. Reaction of cinnoline with trimethylsilyl cyanide and benzoyl chloride gave 1,2-dibenzoyl-4-cyano-1,2-dihydrocinnoline.     

Reissert compound studies. XV. preparation and reaction of the reissert anion at room temperature

The anions (I and II) have been conveniently generated from the parent Reissert compounds in dimethylformamide using sodium hydride. Rearrangements to ketones, alkyl-ations, and participation of I and II in other nucleophilic displacements have been investigated.