Isoindole derivatives from o-diacylbenzenes and aromatic amines

o-Acetylbenzophenone produced yellow 1,2-diaryl-3-(aryliminomethyl)isoindole by the reaction with aromatic amines in the absence of acid. On the reaction of o-diacetylbenzene under the similar condition, three types of yellow products were obtained. The structures of these isoindole derivatives were determined and their formation mechanism was proposed.     

On the Supposed Isoindole Synthesis from o-Tolunitrile

A recent communication¹ in this journal reported the reaction of o-tolunitrile with sodium in tetrahydrofuran to yield a compound, m.p. 123.5–124°, to which was assigned the isoindole structure 1. A plausible mechanism can be written for the formation of 1 involving reductive dimerization of the cyano groups of two molecules of the nitrile, subsequent 1,5-hydrogen shift from a methyl group, disrotatory electrocyclic isoindole ring closure, and finally air oxidation and tautomerization to 1. Nevertheless, the evidence presented did not require an isoindole structure. Moreover, it would be unusual for a primary enamine to survive.     

2-Bromohexafluoroisobutyric acid and its derivatives

Summary 2-Bromohexafluoroisobutyric acid and its derivatives were prepared.     

The gas phase enthalpies of formation of hydrazine, its methylated derivatives, and the corresponding values for ammonia and its methylated derivatives

Hydrazine and some of its methylated derivatives are highly important species. Despite their molecular simplicity and those of the other methylated derivatives, ammonia, and the corresponding amines, there are significant problems with the literature values of their gas phase enthalpies of formation. We present our high level quantum chemical calculations at the G4 level for all of these species.     

Reactions of 2-sulfanylethanol with mucochloric acid and its derivatives

Mucochloric acid reacted with 2-sulfanylethanol in the presence of triethylamine to give 3-chloro-5-hydroxy-4-(2-hydroxyethylsulfanyl)furan-2(5H)-one which underwent acid-catalyzed cyclization to 7-chloro-2,3,4a,6-tetrahydrofuro[2,3-b][1,4]oxathiin-6-one. Likewise, reactions of 5-alkoxy-3,4-dichlorofuran-2(5H)-ones with 2-sulfanylethanol in the presence of triethylamine involved replacement of chlorine in position 4 of the furan ring with formation of the corresponding 4-(2-hydroxyethylsulfanyl) derivatives. The reaction of mucochloric acid with 2-sulfanylethanol in excess aqueous potassium hydroxide resulted in the formation of an acyclic product, 3-(2-hydroxyethylsulfanyl)-2-chloroprop-2-enoic acid. The structure of 7-chloro-2,3,4a,6-tetrahydrofuro[2,3-b][1,4]oxathiin-6-one and 3-(2-hydroxyethylsulfanyl)-2-chloroprop-2-enoic acid was proved by X-ray analysis.     

Complexes of 2-aminopyridine and its substituted derivatives with iodine

Depending on the amount of halogen used, 2-aminopyridine and its ring-substituted derivatives form complexes with 1 or 2 moles of iodine. In the presence of hydriodic acid, one equivalent of acid is included in the complex. 2-Amino-3,5-dibromopyridine forms a complex with 1 mole of iodine even in the presence of excess iodine or in the presence of HI. According to the IR spectra, the iodine in the complexes is coordinated with the ring nitrogen atom.     

Photolysis and Pyrolysis of N-Methyl Isoindole

Near UV. irradiation of N-methyl isoindole ( 1 ) in deaerated solution has yielded two constitutionally isomeric [_π4_s+_π4_s] dimers 3 and 4 (Scheme 2). No transient or stable photoisomers of 1 were detected. The photodimers were reconverted to 1 both by pyrolysis and photolysis. The photocleavage of dimer 3 proceeds (predominantly) by anonadiabatic pathway yielding 1 in its electronic ground state. Prolonged pyrolysis of 1 afforded 11H-indeno [1,2-c]-isoquinoline ( 5 ) as a major product.     

Bromination of 2-acetylthiophene and its derivatives

A new method has been developed for the bromination of thiophene and its derivatives. The method consists in the action of N-bromosuccinimide in acetic anhydride and glacial acetic acid on the thiophene derivatives. In the bromination of 2-acetylthiophene and its derivatives, the bromine replaces the hydrogen atom in the 5 position of the thiophene ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 185–187, February, 1973.     

Relative reactivity in the condensation of 2H-isoindole- and 2H-indazole-4,7-dione derivatives with o-aminobenzenethiol and its derivatives

The effects of substituents on the condensation of o-aminobenzenethiol derivatives with 2H-isoindole- and 2H-indazole-4,7-dione derivatives were studied by competitive reactions.     

Complexation of silver nitrate with imidazolidine-2-thione and its derivatives

The reaction of AgNO₃ with imidazolidine-2-thione (Imt), 1,3-diazinane-2-thione (Diaz) and their derivatives yields complexes of stoichiometry [AgLNO₃] (where L=Imt or Diaz and their derivatives). The C-2 resonances of the Diaz complexes were shifted more from the free ligand positions compared to the Imt complexes, suggesting that the former bind more strongly to Ag¹ than the latter. TMC 2670     

Reactions of 2-mercaptoacetic acid with mucochloric acid and its derivatives

The stable products of reactions of mucochloric acid and some of its ethers with 2-mer-captoacetic acid were synthesized and characterized. The variation of experimental conditions allowed targeted introduction of a sulfur- containing fragment into particular position of the heterocycle: the reaction in aqueous potassium hydroxide gives 3-substituted 2(5H)-furanone the triethylamine additive in nonaqueous solvents facilitates the formation of 4-substituted products, and acid catalysis results in the replacement of the hydroxy (methoxy) group at C(5). (3,4-Dichloro-2-oxo-2,5-dihydrofuran-5-ylthio)ethanoic acid and (3-chloro-5-hydroxy-2oxo-2,5dihydrofuran-4-ylthio)ethanoic acid were characterized by X-ray diffraction; their crystal and gas-phase structures were discussed. The 5-monosubstituted product crystallizes as a racemate, while 4monosubstituted product, as a conglomerate.     

1-Dibutylboryl-2-diphenylphosphinoethene and its derivatives

1-Butyl-1-dibutylboryl-2-diphenylphosphino-2-phenylethene, which exists in the form 1,1,2-tributyl-3,4,4-triphenyT-1-borata-4-phosphoniacyclobut-2-ene, reacts with sulfur, selenium, methyl iodide, and pyridine under mild conditions with ring cleavage. In (2-butyl-2-dibutylboryl-1-phenylethenyl) diphenylphosphine sulfide and selenide, there is a coordinate bond between the thio-or selenophosphoryl group and the boron atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2793–2796, December, 1989.     

Synthesis of 2-azaanthraquinone and its derivatives

The acylation of benzene, toluene, and chlorobenzene with cinchomeronic acid anhydride in the presence of AlCl₃ has given in each case both possible isomers of the corresponding aroylpyridinecarboxylic acid. It was found that the yields of reaction products and their isomeric compositions depend on the conditions of performing the reaction. The intramolecular cyclization of the isomeric keto acids in the presence of 2% oleum has given 2-azaanthraquinone and chlorine derivatives of it.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 514–518, April, 1980.     

2-chloro-2-thio-1,3,2-oxoazaphosphacyclohexane and its derivatives

Conclusions The authors have obtained 2-chloro-2-thio-1,3,2-oxoazaphos-phacyclohexane and studied its reactions with nucleophilic reagents.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 398–400, February, 1968.     

Complexation of palladium cyanide with imidazolidine-2-thione and its derivatives

Summary Pd(CN)₂ reacts with imidazolidine-2-thione (Imt), 1,3-diazinane-2-thione(Diaz), 1,3-diazipnane-2-thione (Diap) and their derivatives to yield complexes of stoichiometry [PdL₂(CN)₂] or [PdL(CN)₂] (L = Imt, Diaz or Diap and L = Imt having N-Me, Et or Pr substituents), which were characterized by elemental analysis, i.r., ¹H and ¹³C n.m.r. spectroscopy. Both mono- and bis ligand complexes are thought to be square planar with the monoligand binding to metal via sulphur (bridging) and the bis ligand via the monodentate thione group. The ¹³C enriched Pd(¹³CN)₂ complex was prepared and the ¹³C n.m.r. recorded. The C-2 resonance of ¹³C n.m.r. of Imt, Diaz or Diap complexes of the copper(I), silver(I), gold(I) and palladium(II) were compared.     

Synthesis of 2-amino-2-cyanoadamantane and its derivatives

Synthetic routes to new amino nitriles with the functional groups at the 2-position of the adamantane core, based on reactions of adamantanonimines with acetone cyanohydrin or of adamantanone cyanohydrin with aliphatic amines, are considered. The products can be used for preparing new biologically active substances, unsymmetrical adamantyl-containing diamines or amino acids.