Reaction of phenylhydrazides of N-acyl-β-phenyl-β-alanine with phosphorus oxychloride

The reaction of N-methyl-N-phenylhydrazides of N-acyl--phenyl--alanine with phosphorus oxychloride is accompanied by cleavage of the C-N bond in the intermediately formed 2-aminoindole derivative and, after splitting out of an amide fragment, leads to 1-methyl-3-benzylidene-2-iminoindoline and nitriles. Pyrimido [4,5-b] indoles — products of cyclization of the corresponding intermediate 2-aminoindole derivatives — were isolated from the reaction mixtures in low yields. The structure of 1-methyl-3-benzylidene-2-iminoindoline was proved by alternative synthesis.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1356–1359, October, 1980.     

Reaction of α-chloro-α-isonitrosoacetone with aminopyridines

2-Amino, 2-amino-3-methyl-, and 4-aminopyridine react with -chloro--isonitrosoacetone at the heteroring nitrogen atom to give salts, which are converted to imidazo[1,2-a] pyridines or, in the case of 4-aminopyridine, to 1-(1-oximino-2-oxopropyl)-4-pyridoneimine when they are treated with alkali. Acetylpyridylurea was obtained from chloroisonitrosoacetone and 2-aminopyridine in pyridine.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1525–1529, November, 1978.     

Heterocyclic analogs of pleiadiene. 59. Reaction of 1-acetonyl- and 1-phenacylperimidinium salts with hydrazine and ammonium acetate

1-Acetonyl-3-methyl- and 1-methyl-3-phenacylperimidinium salts react with hydrazine hydrate to give tetrahydro-derivatives of the hitherto unknown heterocyclic system 1,2,4-triazino[4,3-a]perimidine. On boiling in acetic acid with ammonium acetate, 3-phenacyl- and 3-(2,4-dimethyl)phenacyl-1-methylperidinium salts are converted into 1-methylamino-8-(4-phenylimidazol-1-y1)naphthalenes, with small amounts of 11-methylimidazo[1,2-a]perimidines also being formed.For No. 58, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1389–1395, October, 1986.The author thank V. A. Anisimova for discussions, and N. A. Klyuev and A. I. Chernyshev for obtaining the PMR and mass spectra.     

Reaction of 4-aminoimadazo[4.5-c]pyridin-2-ones with α-bromomethylketones

The reactions of 4-amino derivatives of imidazo[4.5-c]pyridin-2-ones with -bromomethylketones have been studied. Depending on the nature of the reagents and the reaction conditions, either 5-acylmethyl salts of the starting amine or 2-substituted imidazo[4.5-c]imidazo[1,2-a]pyridin-8-ones can be obtained. The latter compounds are also easily obtained by treatment of the 5-acylmethyl salts with alkali.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 227–232, February, 1986.     

Aqueous hydrolysis of 3-[2-(3-methyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazol-1-yl)-ethylamino]-and 3-[2-(5-methyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazol-1-yl)ethylamino]-propanoates

Noncatalytic hydrolysis of methyl 3-[2-(3-methyl-1H-pyrazol-1-y)ethylamino]-and methyl 3-[2-(5-methyl-1H-pyrazol-1-yl)ethylamino]propanoates at 200°C was performed. According to X-ray diffraction data, the resulting acids exist exclusively as salts.     

Cyclic sulfonium salts with S ... O interactions 2. Molecular structures with six-membered rings

1-[2-(N-methylcarbamoyl)phenyl]-3H-2,1-naphto-(1,8-d,e)-oxathiin-1-ium chloride (2), 1-[2-(N-methylcarbamoyl)-phenyl]-2-methyl-3-oxo-3H-1, 2-naphto-(1,8-d,e)-thiazin-1-ium chloride (3), 1-[8-(N-methylcarbamoyl)naphtyl]-2-methyl-3-oxo-3H-1, 2-naphto-(1,8-d,e)-thiazin-1-ium chloride (4) and 1-(8-carboxylatonaphtyl)-2-methyl-3-oxo-3H-1,2-naphto-(1,8-d,e)-thiazin-1-ium dipolar ion (5) cyclic sulfonium salts were prepared and their chemical properties investigated (spirosulfurane-formation, hydrolysis). The molecular structures obtained from x-ray diffraction can be described with a considerably distorted trigonal bipyramidal arrangement of the ligands about the sulfonium center, with O/N—S ... O=apical angles of 173.9, 164.9, 156.6, and 159.0°, as well as with S—O/N apical bond lengths of 1.648, 1.671, 1.664, and 1.682 Å. The structures exhibit relatively short S ... O close contacts with interatomic distances of 2.253, 2.448, 2.795, and 2.619 Å.     

Steric effects in the synthesis of pyrroloindoles from 5-aminoindols

The formation of angular pyrroindoles from 5-aminoindole substitued in the pyrrole ring depends both on the steric requirements of the substituent at the-position of the pyrrole ring, and on the structure of the -hydroxyketone. Significant amounts of the angular pyrroloindole are only formed together with the linear pyrroindole in the reaction of 2-methyl-5-aminoindole with benzoin. In the remaining cases, the linear ring closure of the pyrrole ring predominates.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 55–57, January, 1995.     

Synthesis,nature of electronic transitions,and absorption spectra of the dye based on 4-(methyl-1-{2-[4-(1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)phenyl]-2-oxoethyl}pyridinium bromide

The reaction of 3-(4-bromoacetylphenyl)-1-methylquinolin-2(1Н)-one with pyridine and 4-methylpyridine has afforded the corresponding pyridinium salts. Condensation of 4-methyl-1-{2-[4-(1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)phenyl]-2-oxoethyl}pyridinium bromide with 4-dimethylaminobenzaldehyde has given a new biscyanine dye, 1-{1-[4-(1,2-dihydro-1-methyl-2-oxo-3-quinolinyl)benzoyl]-2-[4-(dimethylamino)-phenyl]ethynyl}-4-{2-[4-(dimethylamino)phenyl]ethynyl}pyridinium bromide. Its electronic spectrum has been analyzed, and quantum-chemical simulation of spatial and electronic structure of its possible isomers has been performed.     

Coordination compounds of hydrazine derivatives with transition metals. Part 27. Coordination chemistry of 4-amino-3-alkyl-5-thio-1,2,4-triazolines and 4-amino-5-oxo-3-thioxo-6-alkyl-2,3,4,5-tetrahydro-1,2,4-triazines

Summary Mono-, bis- and tris-ligand nickel(II) and cobalt(II) complexes with 4 amino-3-alkyl-5-thio-1,2,4-triazolines (HRL) (R=H, Me, or Et) and 4-amino-5-oxo-3-thioxo-6-methyl-2,3,4,5-tetrahydro-1,2,4-triazine (HL') have been prepared and characterized. In these complexes both HRL and HL' are in the neutral thione form. Nickel(II) and cobalt(II) complexes with mononegative thiolate ligands have been also isolated.The reaction of HL' with copper(II) salts in a molar ration of 11 results in the formation of [Cu(HL')X] (X=Cl or Br) and Cu(L')X (X=NO₃ or CH₃COO). However, in the presence of a large excess of HL' the reaction proceeds with partial reduction of Cu^II and both [Cu(HL')X₂] and [Cu(HL')₂]X have been isolated and characterized. The mechanism of copper(II) reduction by HL' is discussed.     

Acylation and Cyclodehydration of Benzofuran-, Benzothiophene-, and Indolyl-3-acetic Acid Arylamides. Synthesis of Novel Benzofuro[2,3-c]-, Benzothieno[2,3-c], and Indolo[2,3-c]pyrilium and Pyridine Derivatives

The acylation of benzo[b]furan-, benzo[b]thiophene, and indolyl-3-acetic acid arylamides using acetic anhydride in the presence of 70% perchloric acid occurs at the -position of the heterocycle to give 2-acetylbenzo[b]furan-, 2-acetylbenzo[b]thiophene, and 2-acetylindolyl-3-acetic acid arylamides. Depending on the amount of perchloric used in the reaction they undergo cyclodehydration to 3-arylamino-1-methylhetero[2,3-c]pyrilium salts and to N-aryl-1-methyl-3(2H)hetero[2,3-c]pyridones.     

Ring contraction of thia(seleno)diazine rings into pyrazoles in the reaction of 3-aryl-10-methyl-2H-1,3,4-thia(seleno)diazino[3, 2-a]benzimidazolium salts with bases

Reaction of 3-aryl-10-methyl-2H-1,3,4-thiadiazino[3,2-a]benzimidazolium salts with triethylamine led to ring contraction of the thiadiazine ring to a pyrazole ring with the formation of a mixture of derivatives of 3-mercaptopyrazolobenzimidazole and di(pyrazolo[1,5-a]benzimidazolyl-3) disulfide. The disulfides were formed exclusively when these salts react with ethanolic alkali. The reaction with potassium carbonate in acetic anhydridegave3-acetylthiopyrazolo[1,5- a]benzimidazoles. 2-Aryl-4- alkylpyrazolo[1, 5- a]benzimidazoles were formed by heating thiadiazino[3,2-a]benzimidazolium salts in formamide and by treating selenodiazino[3,2-a]benzimidazolium salts with potassium carbonate in acetic anhydride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1698–1705, 1992.     

Condensed heterocycles with a thiazole ring. 16. Cyanine dyes based on thiazolo[3,4-a]pyridinium salts

The reaction of 2-(-chlorobenzyl)pyridines with thioacetamide gave 3-methyl-1-arylthiazolo[3,4-a]pyridinium salts, which form cyanines. It was established that the thiazolopyridinium ring in the dyes has high electron-donor character and a great effective length.See [1] for Communication 15.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1274–1277, September, 1988.     

Fusion of 2-(furan-2-yl)thiazole to 1-methyl-1<Emphasis Type="Italic">H</Emphasis>-benzimidazole

Methylation of 5(6)-nitro-1H-benzimidazole with methyl iodide in the presence of potassium hydroxide and N-methylpyrrolidin-2-one gave a mixture of isomeric 1-methyl-5-nitro- and 1-methyl-6-nitro-1H-benzimidazoles which were reduced with tin in concentrated aqueous HCl on heating. The resulting amines reacted with furan-2-carbonyl chloride in N-methylpyrrolidin-2-one to give furan-2-carboxamides which were treated with excess P₂S₅ in pyridine. Oxidation of isomeric furan-2-carbothioamides with K₃[Fe(CN)₆] in alkaline medium afforded a mixture of intramolecular cyclization products, 2-(furan-2-yl)-6-methyl-6H-imidazo[4,5-g][1,3]benzothiazole and 2-(furan-2-yl)-8-methyl-8H-imidazo[4,5-g][1,3]benzothiazole which were separated by column chromatography and identified.     

Quinindines

3-Acyl-4-methyl-1,2-dihydro-4H--quinindines (VI and III) were obtained by acylation of 1,2-dihydro-4H--quinindine (I), obtained from -quinindane methiodide (IV) by the action of alkali with acid chlorides or anhydrides. The IR and UV spectra of these ketones were studied. Quaternary salt V is formed by treatment of I with excess aliphatic acid anhydride.See [1] for communication III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 87–90, January, 1971.     

Synthesis and Some Transformations of 7-(Fur-2-yl)-1-methyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazolo[4,3-<Emphasis Type="Italic">g</Emphasis>][1,3]benzothiazole

N-Methylation of 5-nitro-1H-indazole in a KOH–DMSO system resulted in a mixture of 1-methyl-5(6)-nitroindazoles in a ratio of 1: 2. Reduction of the isomers with tin in concentrated hydrochloric acid afforded pure 1-methyl-1H-indazole-6-amine. Condensation of the latter with furoyl chloride in 2-propanol yielded N-(1-methylindazol-6-yl)furan-2-carboxamide, treatment of which with an excess of P2S5 in anhydrous pyridine gave the corresponding carbothioamide. 7-(Fur-2-yl)-1-methyl-1H-pyrazolo[4,3-g][1,3]benzothiazole was synthesized by Jacobson oxidation of N-(1-methylindazol-6-yl) furan-2-carbothioamide with potassium ferricyanide in an alkaline medium. Some transformations of 7-(fur-2-yl)-1-methyl-1H-pyrazolo[4,3-g][1,3]- benzothiazole such as formylation and acylation were performed.     

Synthesis of cyclic iodonium salts containing an asymmetric carbon atom

We report the synthesis of two iodonium salts with an asymmetric carbon atom in the cation, viz. 3-methyl-10H,10-(4-tolyl)dibenz[b,e]iodinium tetrafluoroborate and the salt of the same cation with the anion of (–)-mono(N--phenylethyl)maleic acid amide as well as the synthesis of 3-methyl-10H-dibenz[b,e]-iodinium tetrafluoroborate.M. V. Lomonosov Moscow State University, Moscow 119899, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1112–1118, August, 1999.     

α-Ferrocenylalkylation of 1,5-Disubstituted Tetrazoles and Certain Transformations of Reaction Products

The reaction of -hydroxyferrocenylalkyl derivatives and vinylferrocene with 1,5-disubstituted tetrazoles in methylene chloride-aqueous acid HX (X = BF4, ClO4) two-phase systems gives a mixture of 1,3,5- and 1,4,5-trisubstituted tetrazolium salts, the fraction of the 1,3,5-isomers prevailing. The synthesized salts are readily dealkylated under the action of bases to give the above starting compounds. Heating of 3(4)-(ferrocenylmethylene)-1,5-pentamethylenetetrazolium and 3(4)-(ferrocenylmethylene)-2-methyl-1-phenyltetrazolium tetrafluoroborates in anhydrous methanol or ethanol in the presence of catalytic amounts of alkali gives rise to ferrocenylcarbinol ethers. Other nuclephiles (pyridine, triphenylphosphine, sodium thiocyanate, sodium p-toluenesulfinate, dibenzoylmethane) also react with the above tetrazolium salts, forming ferrocenylmethylation products. Heating of equimolar amounts of 3(4)-(ferrocenylmethylene)-1,5-pentamethylenetetrazolium or 3(4)-(ferrocenylmethylene)-2-methyl-1-phenyltetrazolium perchlorates with mercury(II) perchlorates in anhydrous ethanol results in mercuration of the starting tetrazolium salts, involving hydrogen substitution in the methylene or methyl groups bound to tetrazolium carbon atoms. The condensation of the same salts with p-N,N-(dimethylamino)nitrosobenzene, leading to azomethine formation, occurs under similar conditions.     

Behavior of propargyl- and allylpropargyl-ammonium salts in aqueous alkaline medium. Synthesis of 2-methyl-2-phenylbenz[f]isoindolinium and 2-methyl-2-phenylisoindolinium salts

Methylphenylpropargyl-(3-phenylpropargyl)-ammonium bromide salts are cyclized almost quantitatively under base-catalysis conditions with the formation of 2-methyl-2-phenylbenz[f]isoindolinium bromide. The allyl analog is subject to rearrangement-decomposition, to a Stevens rearrangement, and to nucleophilic substitution, the cyclic product being obtained in low yield. Methylphenylpropargyl-(3-vinylpropargyl)ammonium bromide is mainly cyclized, but the 3-isopropenylpropargyl analog of this salt is subject to cyclization and subsequent decomposition under analogous conditions.Part 225 of the series on Investigations on Amines and Ammonium Compounds, see [1] for part 224.DeceasedTranslated from Khimiya Geterotsklicheskikh Soedinenii, No. 1, pp. 68–72, January, 1995.     

Investigation of nitrogen- and sulfurcontaining heterocycles

It is shown that 5-acetamido-6-carbethoxymethylmercaptopyrimidines (IV-VII) a r e formed by reaction of 5-amino-6-mercaptopyrimidines (I-IlI) with -chloro- and -chloro--methylacetoacetic esters in the presence of excess alkali, while 6-methyl-7-carbethoxy-pyrimidothiazines (XI-XIII) are formed in the absence of alkali; under similar conditions, hydroxyamino compounds VIII-X and 6-carbethoxymethylpyrimidothiazines XIV-XVI are obtained from I-III and -chloroacetoacetic ester. 6-Carbethoxy- and 7-carbethoxypyrimidothiazines XVII-XXI were synthesized from I-III and ethyl bromopyruvate, II, and chloroformylacetic ester, respectively.For Communication XV, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1423–1427, October, 1970.     

Studies in the imidazole series

By quaternization of 1-alkyl(aryl, aralkyl)-2-methyl-4, 5-diarylimidazoles with -bromo ketones and by subsequent cyclization of the quaternary salts of imidazole, a number of arylpyrrolo[1,2-a]imida~ zoles were obtained. A study was made of the effect of different bases on the process of cyclization and the yield of pyrroloimidazole derivatives. The structure was established of certain intermediate products of the reaction involving the closure of the pyrrole ring.For Part XXXVI, see [11].