Reaction of N1, N2-diarylamidines with chloranil and 2,3-dichloro-1,4-naphthoquinone

Nucleophilic attack by N² of N¹ N²-diarylformamides 1a-c on C-2 of chloranil (2) and subsequently by N¹ on C-1 of 2 initiates the formation of benzimidazolinones 8a-c. In contrast, when 1b-e is reacted with 2,3-dichloro-1,4-naphthoquinone (9) , both chlorine atoms are successively substituted by the two nitrogen atoms and 2-(arylamino)-3-(N-formylarylamino)-1,4-naphthoquinones 13b-e result, which (probably via their cyclic tautomers 12b-e ) may be cyclodehydrogenated to form N¹,N³-diarylnaphtho[2,3-d] imidazoline-2,4,9-triones (as 14b,c ). On the other hand, N¹,N²diarylacetamidines 15a-d attack 2 and 9 at C-2 with N² but subsequently exert nucleophilic character at the acetamidine α-carbon attacking C-1 of 2 and 9 , respectively, thus forming 1-aryl-2-(arylimino)-3a-hydroxy-2,3,3a,6-tetrahydro-1N-indol-6-ones 18a-d and 3-aryl-2-(arylimino)-9b-hydroxy-2,3,5,9b-tetrahydro-1-H-benz[e]indol-5-ones 19b,c , respectively. The latter may be thermally dehydrated to the fully conjugated 2,5-dihydro-3H-benz[e]indol-5-ones 20b,c. Unambiguous structural assignments for 18b and 20c are made on the basis of X-ray crystal structure analyses.     

Reaction of 1,1-dichloro-1-nitrosoalkanes with trimethylchlorosilane and zinc

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, p. 745, March, 1989.     

Reaction of 1,1-dichloro-1-nitrosoalkanes with acid chlorides and zinc

1,1-Dichloro-1-nitrosoalkanes, similar to -halocarbonyl compounds, react with acid chlorides and zinc to give O- acylated acylhydroximoyl chlorides.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 477–478, February, 1990     

Reaction of 1,1-dichloro-1-nitrosoalkanes with trivalent phosphorus acid chlorides

Conclusions 1,1-Dichloro-1-nitrosoalkanes react with trivalent phosphorus acid chlorides not containing a P-O ether bond in the presence of nucleophilic reagents (sulfur dioxide, ethanethiol) to produce phosphorylated alkylchloroformoximes. This is rationalized in terms of intermediate O-alkylchloroformiminoyldichlorophosphorane formation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya., No. 9, pp. 2128–2132, September, 1988.     

Reaction of 1-Phenyl-3,4-dichloro-2-aza-1,3-pentadiene with Triethyl Phosphite

Russian Journal of General Chemistry -     

Reaction ofα,α-dichloro-ω-bromoalkanes andα,α-dichloro-ω-bromoalkenes with benzylmagnesium and allylmagnesium halides

Conclusions The,-dichloro--bromoalkanes and,-dichloro--bromoalkenes react with the benzyl- and allylmagnesium halides in tetrahydrofuran solution to give,-dichloroalkyl(alkenyl)benzenes,,-dichloroalkadienes in high yields. For all practical purposes the reactions do not go in ether.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 886–890, April, 1972.     

Reaction of 4,5-dichloro-3-trichloromethylisothiazole with heterocyclic amines

4,5-Dichloro-3-trichloromethylisothiazole reacted with piperidine, morpholine, pyrrolidine, and piperazine in DMF to give 81–96% of the corresponding 5-amino-4-chloro-3-trichloromethylisothiazoles as a result of selective nucleophilic replacement of the 5-chlorine atom. Acylation of 4-chloro-5-(piperazin-1-yl)-3-trichloromethylisothiazole with acetyl chloride gave 4-chloro-5-(4-acetylpiperazin-1-yl)-3-trichloromethyl-isothiazole.     

Reaction of N,N,N',N'-Tetramethyloxamide with Bromine

Reaction of bromine with N,N,N',N'-tetramethyloxamide results in dibromobromate of 3-methyl-5-dimethylimmoniooxazolidin-4-one (in an open system) and in dibromobromate of 4,5,-dibromo-1,3-dimethylimidazolium (in a closed system).     

Reaction of cyanamides with N,N-binucleophiles

Reactions of 4,6-dimethylpyrimidin-2-yl-and aroylcyanamides with benzene-1,2-diamine, ethylenediamine, cyclohexane-1,2-diamine, and naphthalene-1,8-diamine leads to 1H-benzimidazol-2-amine, imidazolidin-2-imine, perhydrobenzimidazol-2-imine, and 1H-perimidin-2-amine derivatives, respectively.     

Reaction of N,N-Dialkylcarboxamides with Halogens

N,N-Dialkylcarboxamides react with halogens in the absence of water to form complexes which are likely to have an ionic structure with the Hlg⁺ ion coordinated at the carbonyl oxygen atom. These products can be isolated as individual compounds. Complexes with bromine undergo further transformations to afford bis-dialkylamide hydrogen tribromide and the corresponding -bromo amide. When the reaction is carried out in the presence of water, the products are only bis-dialkylamide hydrogen tribromides; here, the N-alkyl groups act as a source of protons.     

Reaction of C,N-diphenylnitrone with N,N-dimethylaminomethylene-P-phenylphosphine

C,N-Diphenylnitrone oxidizes N,N-dimethylaminomethylene-P-phenylphosphine to give dioxophenylphosphorane and dimethylformamide and is reduced to benzalaniline.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1641–1643, July, 1990.     

Reaction of 5-substituted 4,6-dichloro-2-aminopyrimidines with oxalyl chloride

The reaction of 5-substituted 4,6-dichloro-2-aminopyrimidines with oxalyl chloride gives 2-isocyanatopyrimidines, the structures of which were proved by chemical means and the IR, PMR, and ³⁵Cl nuclear quadrupole resonance spectra. The intermediate pyrimidinyloxamic acid chlorides were not isolated; this is evidently explained by the low basicities of 2-amino-pyrimidines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1248–1251, September, 1977.     

Reaction of 4,5-dichloro-3-nitropyridazin-6-one with dimethylchloromethyleneammonium chloride

3,4,5-Trichloropyridazin-6-one, 3,4,5,6-tetrachloropyridzine and 4,5-dichloro-3-(N,N-dimethylamino)-pyridazin-6-one were synthesized from 4,5-dichloro-3-nitropyridazin-6-one and dimethylchloromethylene-ammonium chloride selectively.     

Reaction of N,N-dichlorosulfonamides with aryl isothiocyanates

The reaction of aryl isothiocyanates with the N,N-dichloroamides of arenesulfonic acids and with the morpholide of sulfamic acid has been studied. Instead of the expected products of the oxidative imination of the aryl isothiocyanates, 2-(arylsulfonylamino)benzothiazoles and 2-(morpholinosulfonylamino)benzothiazoles, respectively, were obtained.