E)-1Alkyl4-[2-(alkylsulfonyl)-1-ethenyl]pyridinium Salts: Reaction with Thiol Groups Giving Rise to Chromophoric (E)-1Alkyl4-[2-(alkylsulfanyl)-1-ethenyl]pyridinium Salts (original) (raw)
Syntheses with pyridinium and sulfonium salts of acylated ?-enaminonitriles
Monatshefte f�r Chemie Chemical Monthly, 1995
Pyridinium and sulfonium salts 2a-e which can be prepared from 3-amino-2-(~-haloacetyl)crotonitriles and 3-amino-2-(~-halo-acetyl)-3-phenyl-acrylonitriles react with malononitrile in the presence of a base to 3-amino-2-pyridinio-phenolates 3a,b and 3-amino-2-sulfonio-phenolates 3c-e. In an analogous way, 3-amino-2-(diethyloxyphosphoryl)-phenol 5a and 3-amino-2-(p-tolyl-sulfonyl)phenol 5b have been prepared. 2,3-Diamino-phenoles 6a,b are formed from the pyridinium salts 3a,b. The behaviour of the pyridinium salts 2a,b towards heterocumulenes has been investigated. Cyanamide leads to the (2-amino-4-hydroxy-pyrid-3-yl)-pyridinium salt 8e. Phenylisothiocyanate gives the 3-pyridinio-2-thioxo-pyridin-4-olates 9a,b. Carbon disulfide gives rise to 3-pyridinio-2-thioxo-pyridin-4-olate 10 or 3-pyridinio-2-thioxo-thiopyran-4-olate 11, depending on the substituent at the 6-position. Phenylisocyanate reacts to the pyrimidin-2,4-dione 12 with loss of N-methyl-pyridinium chloride. S-methylation of 9a and cleavage of the pyridine moiety yields the 3-amino-2-methylthio-pyrid-4-one 14. The structures were investigated by 1H and 13C NMR spectroscopy.
Arkivoc
Ethyl (3-cyano-5-ethoxycarbonyl-6-methyl-4-styryl-2-pyridylsulfanyl)acetate was prepared and reacted with hydrazine hydrate in ethanol to give a mixture of (3-cyano-5-ethoxycarbonyl-6-methyl-4-styryl-2pyridylsulfanyl)acetohydrazide and diethyl 3-amino-6-methyl-4-styrylthieno[2,3-b]pyridine-2,5-dicarboxylate. The latter compound was reacted with 2,5-dimethoxytetrahydrofuran to give 3-(1H-pyrrol-1-yl)thieno[2,3b]pyridine analogue which on treatment with hydrazine hydrate in ethanol furnished 5-ethoxycarbonyl-6methyl-3-(1H-pyrrol-1-yl)-4-styrylthieno[2,3-b]pyridine-2-carbohydrazide. Both acetohydrazide and carbohydrazide were used as precursors for the title compounds.
Research on Chemical Intermediates, 2017
The 1,2-, 1,7-, and 1,12-isomers of (Me 2 S) 2 B 12 H 10 (O, M, and P) react with potassium phthalimide in DMF or EtSNa in CH 3 CN/EtOH upon reflux producing the corresponding isomers of [(MeS)(Me 2 S)B 12 H 10 ]-(O 1-, M 1-, P 1-). If excess of either nucleophile is used, [Me 2 SB 12 H 11 ]-(1) and O , M , P can be converted into dianions [MeSB 12 H 11 ] 2-(2) and [(MeS) 2 B 12 H 10 ] 2-(O 2-, M 2-, P 2-). The use of EtSNa is recommended since it facilitates the isolation of products compared to the potassium phthalimide method. When 1 or O, M, P are treated with an excess of an alkali metal (Na, K) in liquid ammonia at-40°C, sulfide 2 or bissulfide dianions O 2-, M 2-, P 2are obtained cleanly and almost instantly. While both the nucleophilic substitution and alkali metal reduction methods are useful for the synthesis of dianions 2, O 2-, M 2-, and P 2-, only the former method is suitable for the synthesis of the sulfide-sulfonium anions O 1-, M 1-, P 1-. The analysis of the 11 B NMR spectra of 1, O, M, P and anions derived from them demonstrated that the spectra of the disubstituted species can be predicted qualitatively, keeping in mind the simple substituent effects obtained from the spectra of monosubstituted anions 1 and 2. Some evidence is found for small partial double bond character of the B-SMe bonds in anions. [MePPh 3 ] + salts of [MeSB 12 H 11 ] 2-(2) and [1-(MeS)-7-(Me 2 S)B 12 H 10 ]-(M 1-) are structurally characterized by single-crystal X-ray diffraction analysis. Crystal data: [MePPh 3 ] 2 [MeSB 12 H 11 ], P2 1 (No. 4), a) 9.243(1) Å, b) 18.272(1) Å, c) 12.548(1) Å,) 103.17(1)°, Z) 2; [MePPh 3 ][1-(MeS)-7-(Me 2 S)B 12 H 10 ], P1 h (No. 2), a) 9.278(2) Å, b) 12.003(5) Å, c) 14.819(7) Å, R) 112.18(4)°,) 105.61(3)°, γ) 92.91(3)°, Z) 2.
Synthesis and Reactions of New Thiazoles and Pyrimidines Containing Sulfonate Moiety
Journal of Heterocyclic Chemistry, 2018
Treatment of 2-tosyloxybenzylidinethiosemicarbazone (2) with active halo compounds afforded thiazoles 3-5. Moreover, reaction of compound 2 with acetic anhydride or dimethylformamide dimethylacetal gave N,N diacetyl 6 and dimethylamino derivatives 7, respectively. Cyclization of thiazole derivatives 3 with some arylidenemalononitriles yielded thiazolo[2,3-d]pyrans 8-12. Multicomponent reaction of 2-tosyloxybenzaldehyde (1) with urea, thiourea, or compound 2 and ethyl acetoacetate or acetylacetone afforded pyrimidines 13-14. The structures of compounds were elucidated by elemental and spectral analyses.
Organic Magnetic Resonance, 1981
The conformational preferences in solution of eight new open-chain and cyclic aromatic sdphides containing pyridine or 1,3,4-thiadiazole nnits have been investigated, parallel to those of some structurally related phenyl sulphides, by means of 'H NMR spectroscopy. The results obtained have shown that replacement of phenyl by the pyridyl or the 1,3,4-thia&azolyl moieties induces slightly different propeller arrangements, ascriied to the higher conjugative tendency of both electron-defiaent heteroaromatic rings, in all open-chain mixed sulphides, in opposition to the skew arrangements observed for phenyl sulphide derivatives. No prominent differences have been found for cydic sulphides, which preferentially adopt the sterically unhindered saddle shape conformation.