Structure of the UV irradiation product of 5-methyl-2-phenyl-1,2,3-diazaphosphole

Conclusion UV irradiation of 5-methyl-2-phenyl-1,2,3-diazaphosphole leads to 4,4-didehydro-bis(5-methyl-2-phenyl-1,2,3-diazaphosphole).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 633–636, March, 1987.The authors thank A. V. Il'yasov and K. M. Enikeev for discussion of the¹³C NMR spectra.     

Reactions of diazaphospholes with isocyanates

Conclusions A new derivative of a two-coordinated phosphorus atom, and specifically 2-acetyl-4-trichloroacetamido-5-methyl-1,2,3-diazaphosphole, was obtained by the reaction of 2-acetyl-5-methyl-1,2,3-diazaphosphole with trichloroacetyl isocyanate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1182–1183, May, 1984.     

Molecular structure of cis-syn-cis isomer of 2,2,6,9-tetramethyl-4,11-diphenyl-4,5,10,11-tetraaza-1,3-diphosphatricyclo[6.3.0.03,7]undeca-5, 9-diene

Conclusions It has been shown by x-ray structure analysis that the interaction of 2-phenyl-5-methyl-1,2,3-diazophosphole with diazopropane forms, along with the cis-anti-cis isomer, the cissyn-cis isomer of 2,2,6,9-tetramethy1-4,11-dipheny1-4,5,10,11-tetraaza-1,3-diphosphatricyclo-[6.3.0.0^3,7]undeca-5,9-diene.Translad from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2023–2028, September, 1984.     

Mechanism of the reactions of diazaphospholes with diazo compounds

Conclusions Diazaphospholes react with diazo compounds by the mechanism of 1,3-dipolar cycloaddition. The reaction of 2-acetyl-5-methyl-1,2,3-diazaphosphole with diphenyldiazomethane proceeds via the intermediate formation of the product of [2 + 3]-cycloaddition.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1376–1380, June, 1987.     

Synthesis and study of 4-aminopyrazolones (5)

Some 4-N-thioureido- and -ureido derivatives are synthesized by reacting 1-phenyl-3-methyl-4-aminopyrazolone(5) hydrochloride at 40–50°, in alcohol solution, with potassium thiocyanate in the presence of sodium acetate plus carbon disulfide, phenylisothiocyanate, and hexamethylenediisocyanate. Acetylation of 1-phenyl-3-methyl-4-aminopyrazolone(5) with C₁–C₈ aliphatic carboxylic acids takes place under more drastic conditions at 100–150°, to give the corresponding 1-phenyl-3-methyl-4-acylaminopyrazolones(5), isolated in 40–60% yield. The UV spectra of the compounds studied are investigated.For Part I, see [1].     

2,5-dimethyl-4-phenylpyridine in the synthesis of substituted indolizines and indeno [2,1-f]indo lizines

The previously unknown 1-acyl-2-aryl(alkyl)-6-methyl-3,7-diphenylindolizines, 2,3-diphenyl-1-acetyl-6-oxo-6H-indeno[2,l-f ]indolizine and 2-methyl-3,6-diphenyl-1-acetyl-6-hydroxy-6H-indeno[2,1-f] indolizine were obtained from 2,5-dimethyl-4-phenylpyridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1220–1223, September, 1972.     

Reactions of compounds containing dicoordinated phosphorus with isocyanates

Conclusions Reaction of 2-acetyl-5-methyl-1,2,3-diazaphosphole with phenyl, trichloroacetyl, anaphthyl, and trimethylsilyl isocyanates gives the 4-substituted diazaphospholes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 169–171, January, 1986.     

Synthesis of 4-acetyl-5(3)-amino-3(5)-methylpyrazoles and pyrazolo[3,4-d]pyrimidines from diacetylketeneN,S-acetal

Isomeric 4-acetyl-5-amino-3-methyl- and 4-acetyl-3-amino-5-methylpyrazoles (2, 3) were formed in the reaction of hydrazines with 3-[amino(methylthio)methylene]pentan-2,4-dione (1) (diacetylketeneN,S-acetal). Pyrazolo[3,4-d]pyrimidines (5a,b) were synthesized by condensation of 4-acetyl-5-amino-1,3-dimethylpyrazole (2a) with amide dimethylacetals followed by treatment with ammonium acetate. The structures of the compounds obtained were confirmed by¹³C and¹⁵N NMR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1429–1433, August, 1993.     

Researches on 2, 1, 3-thia- and selenadiazole

4-Hydroxy-, 4-hydroxy-5-methyl-, 4-hydroxy-7-methylbenzo-2,1,3-thiadiazoles are polymorphous.4-Hydroxybenzo-2,1,3-thiadiazole (I), 4-hydroxy-5-methyl- and 4-hydroxy-7-methylbenzo-2, 1, 3-thiadiazoles (II and III) melt at 114–115°, 110–112°, 100–102° C, respectively, after recrystallization from water [2–4], but after recrystallization from petrol ether [5] they melt at 128–129°, 124–125°, and 119–120° C [5]. In this connection we recrystallized these phenols repeatedly from petrol ether after recrystallizing them from water, and their melting points rose as expected [5]. On the other hand, the compounds with melting points 128–129°, 124–125°, 119–120° C (ex petrol ether), after repeated crystallization from water melted at 114–115°, 110–112°, 100–102° C, respectively.For Part XXXVIII see [1].     

1,3-Dipolar cycloaddition of diazomethane and diazocyclopropane to 2-fluoro-3-methylbutadiene and thermal transformations of fluorine-containing vinylpyrazolines and vinylcyclopropanes

Reactions of 2-fluoro-3-methylbuta-1,3-diene with diazomethane in ether at 15 °C and with diazocyclopropane generated in situ by decomposition of N-cyclopropyl-N-nitrosourea in the presence of K₂CO₃ in CH₂Cl₂ at –10 °C selectively involve the double bond at the methyl group to give 3-(1-fluorovinyl)-3-methylpyrazolines. Thermal dediazotization of the latter at 250 °C yields 1-(1-fluorovinyl)-1-methylcyclopropane and -spiropentane 5, which are capable of isomerizing, under more severe conditions (400—600 °C), into 1-fluoro-2-methylcyclopent-1-ene and 5-fluoro-4-methylspiro[2.4]hept-4-ene (7), respectively. Spiropentane derivative 5 partially isomerizes into 1-fluoro-2-methyl-3-methylidenecyclohex-1-ene. In a similar way, thermolysis of 6-(2,3,3-trifluorocyclobut-1-enyl)-4,5-diazaspiro[2.4]hept-4-ene at 400 °C gives a mixture of 1-(spiropentyl)-2,3,3-trifluorocyclobut-1-ene and 2,3,3-trifluoro-1-(2-methylidenecyclobutyl)cyclobut-1-ene. Thermolysis of 1-cyclopropyl-2,3,3-trifluorocyclobut-1-ene at 550—620 °C affords a mixture of 1-(trifluorovinyl)cyclopentene and 2,3-difluorotoluene.     

Configuration and isomerization of 2,4,5-substituted 1,3,2-dioxaborinanes

Reaction of esters of isobutylboronic acid with 2-methyl-1-phenyl-1,3 propanediol and 2-benzyl-1,3-butanediol gave 2-isobutyl-5-methyl-4-phenyl- and 4-methyl-5-benzyl-1, 3, 2-dioxaborinanes respectively, with a preponderance of the cis-isomers in the mixtures. Cis-2-isobutyl-5-methyl-4-phenyl-1, 3, 2-dioxaborinane was converted to thetrans isomer on heating to 150°C with a catalytic amount of ZnCl₂.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1291–1294, September, 1995.     

Cyclization of N-alkylazinium cations with bifunctional nucleophiles. 16. σ-adducts of quinoxalinium salts with amines,alcohols, and enolates and their role in cyclizations with β-dicarbonyl compounds

In the reaction of N-methylquinoxalinium iodide with acetylacetone at –30 °C, the formation of 3-acetyl-2,4-dimethyl-3a,4,9,9a-tetrahydrofuro[2,3-b]quinoxaline has been recorded by ¹H NMR spectroscopy, this being a regioisomer of the 3-acetyl-2,9-dimethyl-3a,4,9,9a-tetrahydro[2,3-b]quinoxaline formed in this reaction at temperatures above –10 °C. -Adducts of the N-methylquinoxalinium cation with alcohols, amines, and -diketones have also been identified, and their role in cyclizations leading to the annelation of a furan ring is discussed.For Communication 15, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 669–677, May, 1985.     

Stability constants of thorium(IV) complexes with aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl) methane ligands

Summary Stability constants of complexes of aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl) methane [ArBPyM] derivatives with thorium(IV) ions were determined by the potentiometric method at 30°C and an ionic strength of 0.1 mol·dm^–3 (KNO₃) in 75% (v/v) dioxane-water. The evaluation of the titration data indicated that four kinds of complexes ([ThL]²⁺, [ThLOH]⁺, [ThL ₂], and [ThL(OH)₂]^2–) were formed. The formation constants for all [ThL]²⁺ and [ThL ₂] complexes have been calculated to compare these values with those previously reported [1, 2] with Ln³⁺ and UO ₂ ²⁺ metal ions [2, 3]. The probable ligand-bonding sites of the complexes are proposed. In addition, the applicability of theHammett equation for the correlation of the stability constants of [Th(IV)-ArBPyM] complexes are discussed.

---

Stabilitätskonstanten von Thorium(IV)-Komplexen mit Aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl)-methan-Liganden

Zusammenfassung Stabilitätskonstanten von Komplexen von Aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl)-methan — Derivaten [ArBPyM] mit Thorium(IV) — Ionen wurden bei 30°C und einer Ionenstärke von 0.1 mol-dm^–3 (KNO₃) in 75% (v/v) Dioxan-Wasser potentiometrisch bestimmt. Die Auswertung der Titrationskurven zeigte, daß vier verschiedene Komplexe vorlagen ([ThL]²⁺, [ThLOH]⁺, [ThL ₂] und [ThL(OH)₂]²⁺). Die Bildungskonstanten aller [ThL]²⁺- und [ThL ₂]-Komplexe wurden berechnet, um sie mit den früher für Ln³⁺- und UO ₂ ²⁺ -Ionen publizierten zu vergleichen. Potentielle Bindungsstellen der Komplexe für Liganden werden vorgeschlagen. Zusätzlich wird die Anwendbarkeit derHammet-Beziehung auf die Korrelation der Stabilitätskonstanten von [Th(IV)-ArBPyM] — Komplexen diskutiert.

     

Reactions of 3,4-Dichloro-N-R-maleimides with Substituted 2-Thiouracils

Reactions of 3,4-dichloro-N-R-maleimides with substituted thiouracils at 40°C gave a 1:1 mixture of isomers of pyrrolothiazolopyrimidinetriones. Under conditions of thermodynamic control (100°C, 5 h) only pyrrolo[3',4':4,5]thiazolo[3,2-a]pyrimidine-4,6,8-triones were formed, hydrolysis of which followed by decarboxylation gave 5-oxo-5H-thiazolo[3,2-a]pyrimidine-2-carboxamide. The structure of N²-phenyl-6-methyl-5-oxo-5H-thiazolo[3,2-a]pyrimidine-2-carboxamide was confirmed by X-ray crystallography. Analogous cyclization of 3,4-dichloro-N-R-maleimides with 2-thioxoquinazol-4-one also gave a mixture of two isomers which were successfully separated by fractional crystallization.     

Pyrazolo[5,4-h]quinazolines

The reaction of 1-phenyl- and 4-chloro-5-formyl-3-methyl-1-(2-pyridyl)-6,7-dihydroindazoles with carbamidinopyrrolidine, 4-carbamidinomorpholine, creatine, 2-carbamidinopyrazine, and 2-carbamidino-5-trifluoromethylpyridine gives the corresponding 3,8-substituted 1-methyl-4,5-dihydropyrazolo-[5,4-h]quinazolines and with 2-aminobenzimidazole gives 3-phenyl- and 3-(2-pyridyl)-1-methyl-4,5-dihydrobenzo[b]indazolo[4,5-e]imidazolo[1,2-a]pyrimidines.Riga Technical University, Riga LV-1658, Latvia; e-mail; marina@osi.lv . Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 962–965, July, 2000.     

Synthesis and molecular structure of 4-nitro-9-phenyl-1H-and 9-hydroxy-3-oxo-9-phenyl-2,3-dihydro-9H-indeno-[2,1- c ]pyridines and 3,7-diphenyl-3a, 4,5,6-tetrahydroindeno[2,1- c ]isoxazolo[5,4- d ]pyridine

The 4-nitro derivatives and an oxidation by-product, 9-hydroxy-2-methyl-3-oxo-9-phenyl-2,3-dihydro-9H-indeno[2,1-c]pyridine were obtained by the nitration of N-alkyl-9-phenyl-2,3-dihydro-1H-indeno-[2,1-c]pyridines with sodium nitrite in acetic acid. Their molecular structures were studied by X-ray structural analysis. The product of [2+3] cycloaddition, 5-methyl-3,7-diphenyl-3a, 4,5,6-tetrahydroindeno[2,1-c]isoxazolo[5,4-d]pyridine, was obtained by the interaction of 2-chloro-1-hydroxy-2-phenylazomethine with 2-methyl-9-phenyl-2,3-dihydro-1H-indeno[2,1-c]pyridine. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1390–1399, September, 2007.     

Heterocyclic analogs of pleiadiene

1-Methylperimidine adds phenylsodium and phenyllithium to the C=N bond to give 1-methyl-2-phenyl-2, 3-dihydroperimidines. However, if benzophenone is present in the reaction mixture, a mixture of 1-methyl-2-phenylperimidine and l-methyl-2, 4-diphenylperimidine (when phenylsodium is used) or l-methyl-2-phenyl-4-(-hydroxybenzhydryl)perimidine (when phenyllithium is used) is formed. It is assumed that the formation of products involving substitution in the naphthalene ring is associated with the participation of C₆H₅ and (C₆H₅)₂C-O^– radical particles that are formed on reaction of the phenylmetallic compound with benzophenone.See [1] for communication XXIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 697–701, May, 1976.     

Formation of the benzo[f]pyrazolo[3,4-c][1,2,5]-triazepine system in the template reaction of o-amino-o′-halophenylazopyrazoles

The substance isolated from the template cyclization of 4-(2-bromo-4-methyl-1-phenylazo)-5-amino-3-methyl-1-propylpyrazole was identified by spectroscopic methods as 5-(2-bromo-4-methylphenyl)-3,7-dimethyl-1-propyl-1,5-dihydrobenzo[f]-pyrazolo[3,4-c][1,2,5]triazepine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 802–804, June, 1979.     

[3,3]-sigmatropic rearrangement of allyl 2-benzothienyl sulfide

Allyl 2-benzothienyl sulfide at 20–120 °C undergoes a [3,3]-sigmatropic rearrangement to give 3-allylbenzothiophene-2-thiol. The kinetic parameters of the reaction were studied. Under the experimental conditions the thiol undergoes cyclization to give 2-methyl-2,3-dihydrobenzothieno[2,3-b]thiophene, 2-methyl-benzothieno[2,3-b]thiophene, and benzothieno[2,3-b]dihydrothiopyran. Allyl 3-methyl-2-benzothienyl sulfide does not form a thiol even at 150–190 °C but rather forms only bis(3-methyl-2-benzothienyl) disulfide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 615–618, May, 1981.     

Formation of 1-(2-aminophenyl)-5-ethoxy-4-methyl-3-phenylpyrazole and 4-methyl-3-phenylpyrazolo-[5,1-b]benzimidazole via an unusual enzotriazole ring opening

Successive treatment of N-[(1-ethoxy)alken-2-yl]benzotriazoles VII with butyllithium and trimethylsilyl chloride in TH-Fat — 78°C followed by refluxing in acidic acetone generated ring-opened 1-(2-aminophenyl)-5-ethoxy-4-methyl-3 phenylpyrazole VIII and 4-methyl-3 phenylpyrazolo[5, 1-b]benzimidazole IX.Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 775–780, June, 1996. Original article submitted May 14, 1996.