REAKTIONEN VON THIOXOHETEROCYCLEN MITN-CHLORAMIDEN II.1N-SUBSTITUIERTE 2- ODER 4-THIOPYRIDONE UND NATRIUM-N-CHLORBENZOLSULFONAMIDE

Boberg, Friedrich; Bruchmann, Bernd; Nink, Gunter; Garming, Alfons

doi:10.1080/10426508908040618

Cited by 13 publications

(4 citation statements)

References 33 publications

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“…Sulfonamido derivatives 7 − 9 were previously unknown in the literature, with the exception of the tosylate 8 , which was reported in very few cases . The general procedure we have followed for the synthesis of 7 and 8 implied condensation of the amine 12 with the proper sulfonyl chloride.…”

Section: Resultsmentioning

confidence: 99%

“…A solution of methyl triflate 0.33 g, 2.0 mmol) in anydrous DMF (2 mL) was then added dropwise to the ice-cooled mixture. After the mixture was stirred for 48 h at room temperature, the milky precipitate was collected, washed with water, and dried over CaCl 2 at reduced pressure to give the practically pure product as a white solid (0.20 g 0.8 mmol, 40%): mp 238−242 °C (lit 20a…”

Section: Methodsmentioning

confidence: 99%

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Pyridoneimines and Pyridonemethides: Substituent- and Solvent-Tunable Intramolecular Charge Transfer and Geometric Isomerism

Abbotto¹,

Bradamante²,

Pagani³

2001

J. Org. Chem.

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We have prepared and fully characterized by means of multinuclear NMR and UV-vis spectroscopy a series of pyridoneimines and pyridonemethides in order to show how it is possible to finely tune pi-electron structure properties by properly exploiting substituent and solvent effects. Substituents with different electron-withdrawing capacities were introduced in pyridoneimines 2-4, pyridonemethides 5 and 6, and pyridine sulfonamido derivatives 7-9. The anisochrony of the carbon position of the azinium ring (geometric isomerism) and the exploitation of previously reported (13)C and (15)N shift/pi-electron density relationships allowed the investigation of the extent of intramolecular charge transfer from the donor group to the acceptor pyridinium moiety. By combining different substitutions with the polarity of the surrounding media, we were able to access a whole range of push-pull electron structures in solution, from fully aromatic-zwitterionic to quinoid-neutral, through many possible intermediate situations along the path. Due to the strict correlation between the pi-electron structure of push-pull derivatives and many photonic properties such as nonlinear optical activity, we believe that the achieved results should be valuable for the development of new efficient, tailor-made, heteroaromatic systems with optimized features as advanced organic materials.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Pyridoneimines and Pyridonemethides: Substituent- and Solvent-Tunable Intramolecular Charge Transfer and Geometric Isomerism

Abbotto¹,

Bradamante²,

Pagani³

2001

J. Org. Chem.

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“…The stable sulfinimide (la) also reacted with norbornene to form the tricyclic compound (5b). The 4-thia-3-azatricyclo-[ 5.2.1 .02.6]decan-5-ene derivatives (5) are formed as a result of HCI elimination from the primary adduct (4). The maximal yields of compounds (5) were obtained when triethylamine was used to bind the evolving hydrogen chloride.…”

Section: Resultsmentioning

confidence: 99%

N‐alkyl‐C‐polyfluoroalkyl‐C‐chlorosulfinimides R_FC(Cl)SNR

Ahlemann

Roesky

Markovsky

et al. 1995

Heteroatom Chemistry

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“…There are several types of sulfinimides in which the ylide carbon atom is the part of an aromatic [3], alicyclic [4] or heterocyclic system [5] and is connected with electronwithdrawing arylsulfonyl [6] or trifluoromethyl [2,7] groups. Earlier we reported the first sulfinimides containing perfluoroalkyl substituents and a chlorine atom at the ylide carbon atom : N-alkyl-C-polyfluoroalkyl-C-chlorosulfinimides (3) [8].…”

Section: Introductionmentioning

confidence: 99%

5‐Chloro‐5‐trifluoromethyl‐3‐aryl‐4‐alkyl(aryl)‐isothiazolidines and their Dehydrochlorination Reactions

Solov'ev

Chernega

Almsick

et al. 2005

Zeitschrift anorg allge chemie

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N-Alkyl(aryl)-C-trifluoromethyl-C-chlorosulfinimides and styrenes react to give the 3ϩ2 cycloaddition products, 5chloro-5-trifluoromethyl-3-aryl-4-alkyl(aryl)-isothiazolidines 9a-h. The structure of the dehydrochlorination products derived from the compounds 9a-h is determined by the nature of the substituent near the nitrogen atom. The compounds having bulky tertiary-butyl group (9c,h) are transformed into the isothiazolines derivatives 10a,b, but compounds 9a,b,d-g form β-aminovinyl trifluoromethylthioketones 11a-f.The nature of the substituent near the nitrogen atom in the molecule 9 influences not only the thermal stability of the isothiazolidines but also their transformations during dehydrochlorination.Compounds 9c,h with a tertiary-butyl substituent near the nitrogen atom form isothiazolidines 10a,b upon heating with triethylamine in toluene. All the other isothiazolidine derivatives 9a,b,d-g are transformed into b-aminovinylthioketones 11a-f under the same conditions, meaning that hydrogen chloride elimination is accompanied by isothiazoline cycle opening.Examples of the isothiazoline cycle S-N bond rupture upon attack of nucleophilic reagents on the sulfur atom are known in the literature [12]. It may be assumed that the difference in the dehydrochlorination results for compounds 9 is caused by the shielding effect of the tertiary-butyl substituent, which prevents the attack on the sulfur atom in isothiazolines 10a,b by chloride ion. In contrast to this, the attack is possible in the isothiazolines 12, intermediately formed by dehydrochlorination of the compounds 9a,b,d-g. This attack results in the rupture of the sulfur-nitrogen bond and formation of thioketones 11a-f.Fluorine-containing thioketones 11c,e are red crystalline compounds and thioketones 11a,b,d,f are viscous red liquids which were purified by chromatography on silicagel. The first thioketones of this type were obtained as a result of β-aminovinylketones thionation [13].An apparently anomalous low-field chemical shift in the 1 H NMR spectra for the proton connected to nitrogen of compounds 11a-f (ϳ15 ppm) is noteworthy (see experimental part and [13]). The investigation of the structure of compound 11e by single-crystal X-ray diffraction allowed us to determine the reason of such a low-field δ NH value.

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REAKTIONEN VON THIOXOHETEROCYCLEN MITN-CHLORAMIDEN II.¹N-SUBSTITUIERTE 2- ODER 4-THIOPYRIDONE UND NATRIUM-N-CHLORBENZOLSULFONAMIDE

Cited by 13 publications

References 33 publications

Pyridoneimines and Pyridonemethides: Substituent- and Solvent-Tunable Intramolecular Charge Transfer and Geometric Isomerism

Pyridoneimines and Pyridonemethides: Substituent- and Solvent-Tunable Intramolecular Charge Transfer and Geometric Isomerism

N‐alkyl‐C‐polyfluoroalkyl‐C‐chlorosulfinimides R_FC(Cl)SNR

5‐Chloro‐5‐trifluoromethyl‐3‐aryl‐4‐alkyl(aryl)‐isothiazolidines and their Dehydrochlorination Reactions

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REAKTIONEN VON THIOXOHETEROCYCLEN MITN-CHLORAMIDEN II.1N-SUBSTITUIERTE 2- ODER 4-THIOPYRIDONE UND NATRIUM-N-CHLORBENZOLSULFONAMIDE

Cited by 13 publications

References 33 publications

Pyridoneimines and Pyridonemethides: Substituent- and Solvent-Tunable Intramolecular Charge Transfer and Geometric Isomerism

Pyridoneimines and Pyridonemethides: Substituent- and Solvent-Tunable Intramolecular Charge Transfer and Geometric Isomerism

N‐alkyl‐C‐polyfluoroalkyl‐C‐chlorosulfinimides RFC(Cl)SNR

5‐Chloro‐5‐trifluoromethyl‐3‐aryl‐4‐alkyl(aryl)‐isothiazolidines and their Dehydrochlorination Reactions

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REAKTIONEN VON THIOXOHETEROCYCLEN MITN-CHLORAMIDEN II.¹N-SUBSTITUIERTE 2- ODER 4-THIOPYRIDONE UND NATRIUM-N-CHLORBENZOLSULFONAMIDE

N‐alkyl‐C‐polyfluoroalkyl‐C‐chlorosulfinimides R_FC(Cl)SNR