Reactions of 3-acycloxysulfolanes with nucleophilic reagents

In contrast to alkyl esters of carboxylic acids, 3-acyloxysulfolanes on reaction with nucleophilic reagents readily split out a carboxylic acid to give 2-sulfolene, which then reacts with compounds containing a labile hydrogen atom. On the basis of data on the kinetics of alkaline hydrolysis of benzoates, a scheme for elimination of the acid that includes the intermediate formation of a transition state of the E₁CB type is proposed.     

Reactions of substituted phenazine salts with nucleophilic reagents

The condensation of 1-chloro-, 1-phenyl-, 3-chloro-, 3-cyano-, and 3,7-dimethoxy-substituted phenazinium salts with malonic and cyanoacetic esters, N-methylrhodanine, 2-methylbenzothiazolium and quinaldinium salts, aniline, and morpholine was studied. The absorption spectra of the synthesized dyes are described.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1425–1429, October, 1972.     

Reactions of (difluoroamino)trinitromethane with nucleophilic reagents

Reactions of F₂NC(NO₂)₃ with metal fluorides (KF and CsF) in DMF yield a substitution product of the fluorine atom for one nitro group, F₂NC(NO₂)₂F. The reaction of F₂NC(NO₂)₃ with LiBr in ethanol or DMF affords Br(NO₂)C=NF rather than the expected bromo derivative F₂NC(NO₂)₂Br.     

Reactions of 2-pyrimidinyl phosphites with proton-containing nucleophilic reagents

Conclusions The reaction of 4,6-dimethyl-2-pyrimidinyl phosphites with proton-containing nucieophilic reagents is due to the anhydride nature of the C_pry-O-P bond and proceeds with the formation of 4,6-dimethyl-1,2-dihydro-2-pyrimidone and the corresponding P(III) derivatives.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 159–162, January, 1986.     

Reactions of 1-aryl-2-bromo-3,4,4-trichlorobut-3-en-1-ones with some nucleophilic reagents

Reactions of 2-bromo-1-phenyl- and 2-bromo-1-(4-methylphenyl)-3,4,4-trichlorobut-3-en-1-ones with morpholine and diethylamine are accompanied by prototropic allylic rearrangement, leading to 3-amino-1-aryl-2-bromo-4,4-dichlorobut-2-en-1-ones as mixtures of E and Z isomers. The title compounds react with hydrazine, hydroxylamine, and thiourea to give the corresponding 5-aroyl-4-methoxypyrazoles, 3-aryl-5-hydroxyiminomethyl-4-methoxyisoxazoles, and 2-amino-4-aryl-5-trichlorovinylthiazoles.     

Reactions of 1,3,5-tris(fluorosulfonyl)benzene with some nucleophilic reagents

The reactions of 1,3,5-tris(fluorosulfonyl)benzene 1 with nucleophilic agents were investigated. It was found that morpholine, β,β,β-trifluoroethanol in the presence of triethylamine and sodium azide formed corresponding 1,3,5-trisulfonyl derivatives. In contrast, nucleophiles such as aniline, thiourea, and potassium thiocyanate do not react with compound 1 even in excess and under moderate heating. The conditions for the selective fluorine atom substitution in one SO₂F group with morpholine, DMAP and aniline in the presence of triethylamine as well as in two SO₂F groups with DMAP were found. Anionic σ-complex of compound 1 with nitromethane was isolated as individual compound.     

Reactions of quaternary salts of benzo derivatives of phenazine with nucleophilic reagents

The electronic structures of benzo[a]phenazine and dibenzo[a,c]phenazine have been studied by the MO LCAO method. The reactions of four quaternary salts with oxomethylene compounds and with quaternary salts of nitrogenous heterocycles have been described. The absorption spectra of the dyes obtained are given.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1552–1557, November, 1973.     

Reactions of 4-methyl(chloro)sulfonyl-2,3,5,6-tetrabromopyridines with nucleophilic reagents

The MeSO₂ group is replaced in the reaction of 4-methylsulfonyltetrabromopyridine with small nucleophiles, whereas the Br atom in the 2 position is replaced in the reaction with bulky nucleophiles. Depending on the temperature conditions and the ratio of the reacting substances, 4-chlorosulfonyltetrabromopyridine reacts with primary amines to give either the corresponding amides or amines. It was established that the corresponding amines are formed when tetrabromopyridinesulfonic acid -hydroxyalkylamides are heated with triethylamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 937–942, July, 1979.     

Reactions of 4-acyl-1-alkoxyaryl-5-aryl-3-hydroxy-2,5-dihydro-1H-pyrrol-2-ones with nucleophilic reagents

4-Acetyl-1-alkoxyaryl-5-aryl-3-hydroxy-2,5-dihydro-1H-pyrrol-2-ones reacted with amines to give 1-alkoxyaryl-5-aryl-4-(1-R-aminoethylidene)pyrrolidine-2,3-diones. Reactions of amines with 4-benzoyl-substituted analogs involve nucleophilic attack on the C³ atom in the heteroring to produce the corresponding 3-R-amino-1-alkoxyaryl-5-aryl-4-benzoyl-2,5-dihydro-1H-pyrrol-2-ones. Reactions of the title compounds with hydrazine hydrate, regardless on the substituent on C₄, afforded 4-aryl-3-methyl(phenyl)-5-[2(4)-methoxyphenyl]-4,6-dihydropyrrolo[3,4-c]pyrazol-6-ones.     

Reactions of 1-arylthioniacycloalkane salts with nucleophilic agents

Depending on the structures of the salt and the nucleophilic agent, replacement of the anion of the sulfonium salt or expansion of the heteroring at the C-S bond to give substituted alkyl aryl sulfides occurs in the reaction of 1-(p-hydroxyphenyl)- and 1-(p-methoxyphenyl)thioniacyclopentane (I, III) and -thioniacyclohexane perchlorates (II, IV) in aqueous or alcohol solutions with potassium halides and potassium hydroxide. The ease of cleavage of the C-S bond as a function of the nature of the nucleophilic agent decreases in the order KOH > Cl > Br. The strength of the C-S bond of the heteroring decreases in the order II > I >IV > III. All of the heterocycles (I–IV) are stable with respect to the action of picric acid and potassium iodide, and 1-(p-hydroxyphenyl)thioniacyclohexane perchlorate (II) is stable with respect to the other investigated nucleophiles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1032–1038, August, 1978.     

Reactions of polyhalopyridines 5. Reaction of 2,3,5,6-tetrachloro-4-trifluoromethylthiopyridine with nucleophilic reagents

The reaction on 2, 3, 3, 6-tetrachloro-4-trifluoromethylthiopyridine with various nucleophilic reagents has been studied. It was shown that the CF₃S group is readily replaced under the action of O- and S-nucleophiles. Competition was detected between replacement of an a-chlorine atom on the pyridine ring and of the fluorinecontaining group under the action of N-nucleophilic reagents. New derivatives of trichlorotrifluoromethylthiopyridine with nitrogen-containing substituents have been synthesized.For Communication 4 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 63–67, January, 1994.     

Reactions of esters of tetracoordinated phosphorus acids with nucleophilic reagents in highly organized media

Characteristic features of reactions involving esters of phosphorus-containing acids in highly organized media (micelles, liquid crystals, vesicles, and emulsions) are surveyed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 298–312, February, 1996.     

Reactions of (chlorodifluoromethyl)benzene and (chlorodifluoromethoxy)benzene with nucleophilic reagents

Condensation reactions of (chlorodifluoromethyl)benzene and (chlorodifluoromethoxy)benzene with phenoxide and thiophenoxide ions have been performed in DMF or NMP with heating. In these conditions, the reaction between phenylselenide ion and (chlorodifluoromethyl)benzene did not occur. This latter reaction requires an additional visible light irradiation to proceed, as reported by Yoshida et al.     

Reaction of anthrapyridones with nucleophilic reagents

The present authors previously showed that anthrapyridone (7H-dibenz [f, ij] isoquinoline-2, 7 [3H] dione) (I) and N-methylanthrapyridone (II) react with aliphatic amines to give the corresponding 1-alkylaminoanthrapyridones [1]. Continuing the research, the reaction of anthrapyridones with other nucleophilic reagents has been studied. Boiling N-methylanthrapyridone with an aqueous dioxane solution of sodium hydroxide, gave a 50% yield of a compound which, after recrystallization from acetic acid had mp 299–300° C (decomp). Found: C 73.57, 73.71; H 3.80, 3.85; N 5.00, 5.22%. Calculated for C₁₇H₁₁NO₃: C 73.62; H 4.00; N 5.05%. The compound was identical in chemical properties, melting point, and IR spectrum with 1-hydroxy-N-methylanthrapyridone(III), prepared by the action of ethanolic alkali on 1-chloro-N-methylanthrapyridone(IV) by the method of [2].