Reaction of 2-(4-Arylthiazol-2-yl)-4-chloro-3-oxobutyronitriles with Secondary Aliphatic Amines

We have obtained 2-(4-arylthiazol-2-yl)-4-chloro-3-oxobutyronitriles by acylation of 4-aryl-2-cyanomethylthiazoles with -chloroacetyl chloride. We have studied their reaction with secondary aliphatic amines, leading to formation of 4-dialkylamino-2-(4-arylthiazol-2-yl)-3-oxobutyronitriles, and also intramolecular alkylation with formation of 3-aryl-7-cyano-6(5H)-oxopyrrolo[2,1-b]thiazoles. We have determined some aspects of the tautomerism of the synthesized compounds.     

Synthesis of 1-(1-Adamantyl)-2-hydroxy-3-amino-3-R-propanones

Previously unknown cis-1-(1-adamantyl)-2,3-epoxy-3-R-propanones were highly selectively obtained by epoxidation of ,-unsaturated ketones with hydrogen peroxide in alkaline medium. The regioselectivity of the epoxide ring cleavage with amines (piperidine and morpholine) was studied.     

Synthesis of 1-aryl-5-chloro-3-(phenylsulfonyl)pyrazol-4-ols from 1,1-dichloro-3-phenylsulfonyl-2-propanone

1,1-Dichloro-3-phenylsulfonyl-2-propanone was treated with arenediazonium chlorides to give 1-arylhydrazono-3,3-dichloro-1-phenylsulfonyl-2-propanones, which were cyclized to 1-aryl-5-chloro-3-(phenylsulfonyl)pyrazol-4-ols on treatmemt with base.     

Three-Component Reaction of 1-(Oxyran-2-ylmethyl)-1 H -indole-3-carbaldehyde with CH-Acids and Amines

One-pot synthesis of 3-vinyl substituted indoles containing 1,2-amino alcohol fragment at the nitrogen atom was performed by the reactions of 1-(oxiran-2-ylmethyl)-1H-indole-3-carbaldehyde with methylene-active compounds and amines.     

Reaction of 3,4,4-Trichloro-1-(4-methylphenyl)-3-buten-1-one with Amines

Reaction of 3,4,4-trichloro-1-(4-methylphenyl)-3-buten-1-one with amines results in replacement of the internal chlorine atom and is accompanied by prototropic allyl rearrangement leading to formation of the corresponding 3-amino-4,4-dichloro-1-(4-methylphenyl)-2-buten-1-ones. The reaction of the title compound with 2,4-dinitrophenylhydrazine yields 3,4,4-trichloro-1-(4-methylphenyl)-3-buten-1-one 2,4-dinitrophenylhydrazone and is not accompanied by allyl rearrangement.     

1-(1-Adamantyl)diaziridine

The reaction of 1-aminoadamantane with CH₂O and H₂NOSO₃H in the presence of K₂CO₃ under phase-transfer conditions leads to hitherto unknown 1-(1-adamantyl)diaziridine and (1-adamantyl)aminoacetonitrile, characterized by spectral data. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 861–862, April, 1997.     

Syntheses of Heterocycles from the Sodium Salts of 3-(1-Adamantyl)-1-hydroxy-1-propen-3-one and 4-(1-Adamantyl)-1-hydroxy-1-buten-3-one

The interaction of the sodium salts of 3-(1-adamantyl)-1-hydroxy-1-propen-3-one and 4-(1-adamantyl)-1-hydroxy-1-buten-3-one with hydroxylamine, hydrazine, and guanidine leads to the synthesis of 5-(1-adamantyl)-5-hydroxy- and 5-(1-adamantylmethyl)-5-hydroxy-2-isoxazolines, 3-(1-adamantyl)- and 3-(1-adamantylmethyl)pyrazoles, 3-(1-adamantyl)-2-phenylpyrazole, and 4-(1-adamantyl)-2-amino- and 4-(1-adamantylmethyl)-2-aminopyrimidines.     

Reaction of 2-(4-alkylpiperazino)-3-chloro-1,4-naphthoquinones with sodium azide

It was shown that 2-(4-alkylpiperazino)-3-chloro-1,4-naphthoquinones react on heating with NaN₃ in DMF to form new heterocyclic quinones — 1,2,3,4-tetrahydro-13-alkyl-3,1-(iminoethano)benzo[g]quinoxaline-5,10-diones as well as the corresponding 2-(4-alkylpiperazino)-3-aminonaphthoquinones and naphthimidazopyrazinediones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2103–2107, September, 1990.     

Reaction of 3-chloro-3-sulfolene and 3-chloro-2-sulfolene with alkyl(aryl)amines

The corresponding 3-alkylamino-2-sulfolenes are formed in the reaction of 3-chloro-3-sulfolene and 3-chloro-2-sulfolene with aliphatic amines. It was established that under the influence of the amines 3-chloro-3-sulfolene initially undergoes isomerization to 3-chloro-2-sulfolene with subsequent replacement of the chlorine atom by the amine component. 3-Chloro-3-sulfolene and 3-chloro-2-sulfolene are inert in the reaction with aromatic amines that have low basicities.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 892–894, July, 1979.     

Hydrolysis Reactions and Resolution of (±)-2-Acetamido-3-hydroxy-1-(4-nitrophenyl)-1-propanone

IntroductionChloramphenicol,which was isolated fromStreptomyces venezuelae in 1 947[1] ,is used as abroad- spectrum antibiotic possessing activityagainst many Gram- negative and Gram- positivemicroorganisms. (± ) - 2 - Acetamido- 3 - hydroxy- 1 -(4- nitrophenyl) - 1 - propanone[(± ) - 1 ]is one of theintermediates of producing chloramphenicol.Petrow et al.[2 ] reported some transformations of(± ) - 1 in hydrolysis reactions. However,thereaction products were complicated under multiplehydr…     

Reaction of 2-(2-Azahetaryl)-4-chloro-3-oxobutyronitriles with Substituted Benzaldehyde Hydrazones. Unexpected Formation of 4-Arylideneamino-2-(1-R-benzimidazol-2-yl)-3-oxobutyronitriles

The reaction of 2-(2-azahetaryl)-3-oxo-4-chlorobutyronitriles with substituted benzaldehyde hydrazones gives 4-arylideneamino-2-(1-R-benzimidazol-2-yl)-3-oxobutyronitriles, the structures of which were proved using spectroscopic data, the results of elemental analysis, and through their chemical reactions. It was found that the reaction course depends on the basicity of the heterocyclic fragment in the starting nitrile. A likely mechanism for the process is proposed.     

Nucleophilic Vinylic Substitutions of (E)- and (Z)-Ethyl 3-Aryl-3-chloro-2-cyanopropenoates with Primary and Secondary Amines

Some new (Z)-ethyl 3-amino-3-aryl-2-cyanopropenoates have been prepared in good yields by reacting (E)- and (Z)-ethyl 3-aryl-3-chloro-2-cyanopropenoates with primary and secondary amines. The (Z)-isomers were exclusively formed.although the starting material consisted of a mixture of (E)- and (Z)-isomers (≈ 1:1)     

Synthesis of 1-aryl-5-arylazo-3-phenylsulfonylpyrazol-4-ols from 1-chloro-3-phenylsulfonyl-2-propanone

Treatment of 1-chloro-3-phenylsulfonyl-2-propanone (2) with arenediazonium chlorides gave 1-arylhydrazono-3-chloro-1-phenylsulfonyl-2-propanones 4 , which were cyclized in the presence of sodium acetate to 1-aryl-3-phenylsulfonylpyrazol-4-ols 5B. Further treatment of 5B with arenediazonium chlorides yielded 1-aryl-5-arylazo-3-phenylsulfonylpyrazol-4-ols.     

Functionalization of the Methyl Ketone Fragment in 1-[(1S,3R)-2,2-Dimethyl-3-(2-methoxymethyloxyethyl)cyclopropyl]-2-propanone

Deprotonation of 1-[(1S,3R)-2,2-dimethyl-3-(2-methoxymethyloxyethyl)cyclopropyl]-2-propanone with lithium diisopropylamide in THF at -78°C and subsequent treatment of the resulting enolate with Me₃SiCl yielded mainly the corresponding terminal silyl enol ether. The condensation of intermediate enolate with benzaldehyde regioselectively afforded a mixture of the corresponding aldol and its dehydration product. The reactions of the title ketone with NBS, as well as of the silyl enol ethers derived therefrom with I₂, led to formation of mixtures of products via opening of the cyclopropane ring.     

Rearrangement in the series of 3-(2-aryl-2-oxoethyl)-3,4-dihydroquinoxalin-2(1H)-ones

4-Acetyl- and 4-succinyl-3-(2-aryl-2-oxoethyl)-3,4-dihydroquinoxalin-2(1H)-ones undergo the rearrangement into (Z)-2-(3-arylquinoxalin-2-ylidene)acetic acids accompanied by the elimination of the acyl groups. The nitration of 3-(2-oxo-2-phenylethyl)-3,4-dihydro-quinoxalin-2(1H)-one affords 5-nitro- and 7-nitro-2-carboxymethylidenequinoxalines. The bromination of quinoxalin-2-ones in AcOH gives 3-aryl-2-carboxymethylidenequinoxalines and the corresponding 7-bromo derivatives, with the former products predominating.     

Synthesis of new modified aza heterocycles on the basis of 5-(2-chloro-1-nitroalkyl)-3-phenyl-and 5-(2-chloro-1-nitroalkyl)-3-methyl-1,2,4-oxadiazoles

3-Phenyl-and 3-methyl-5-(2-chloro-1-nitroalkyl)-1,2,4-oxadiazoles reacted with piperidine, pyrrolidine, and morpholine to give the corresponding 5-(2-amino-1-nitroalkyl) derivatives, while their reactions with sodium p-toluenesulfinate led to the formation of 2-[3-methyl(or phenyl)-1,2,4-oxadiazol-5-yl]-2-nitroethyl p-tolyl sulfones.