Tetrathiatetraza-azulene; synthesis and X-ray crystal structure

Jones, Ray; Morris, Janet L.; Rees, Charles W.; Williams, David J.

doi:10.1039/c39850001654

Cited by 15 publications

(11 citation statements)

References 3 publications

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“…In one stack adjacent molecules are rotated by 180 with respect to each other, whilst in the other they are rotated by 80 to each other. 8 The highly delocalised nature of the azulene 4 is further supported by its thermal stability; it remains substantially intact after 7 h at reflux in toluene. However, it is significantly decomposed at reflux in toluene in the presence of either S 4 N 4 (20% recovery after 7 h) or phenyl vinyl sulfoxide (42% recovery after 7h), and this presumably contributes to the relatively low yield.…”

Section: Resultsmentioning

confidence: 93%

“…Acetylene has thus become incorporated into the S 4 N 4 structure but with its hydrogen atoms removed; however S 4 N 4 is known to be able to act as a dehydrogenating agent. [4][5][6][7][8][9] The thermal stability and spectroscopic properties of the new product suggested an aromatic structure in which the alternating arrangement of sulfur and nitrogen atoms of S 4 N 4 had been retained; three possible structures are 4, 5, or 6. A single crystal X-ray analysis showed the product to be 1 λ4δ2 ,3,5,7 λ4δ2 -tetrathia-2,4,6,8-tetraza-azulene 4.…”

Section: Resultsmentioning

confidence: 99%

“…In a preliminary publication 8 we reported that when S 4 N 4 (2 equiv.) was heated with the sulfoxide 3 (1 equiv.)…”

Section: Resultsmentioning

confidence: 99%

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Tetrathiatetraza-azulene

English¹,

Morris²,

Rees³

2000

Arkivoc

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Dedicated with warm regards to Professor Gurnos AbstractTetrasulfur tetranitride 1 reacts with phenyl vinyl sulfoxide 3 or sulfone or phenyl vinyl sulfonate to give the planar delocalised 14 P electron aromatic system 1 λ4δ2 , 3,5,7 λ4δ2 -tetrathia-2,4,6,8-tetraza-azulene 4 as stable dark metallic lustrous crystals. All the sulfur and nitrogen atoms of S 4 N 4 have been retained and a C-C P bond incorporated, the 12 P cage structure of S 4 N 4 being converted into the planar bicyclic system. A mechanism is proposed for this transformation. The ability of the vinyl component to act as an acetylene equivalent and to suffer dehydrogenation to give the aromatic product appear to be necessary for this type of reaction since more highly substituted sulfoxides lead only to decomposition. Optimum conditions for the reaction of phenyl vinyl sulfoxide with S 4 N 4 (3.6 equiv.) in refluxing xylene for 7.5 h give the tetrathiatetrazaazulene 4 in 35%.

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Section: Resultsmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

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Tetrathiatetraza-azulene

English¹,

Morris²,

Rees³

2000

Arkivoc

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“…Thus, tetrasulfur tetranitride and phenyl vinyl sulphoxide reacted to give the planar delocalized 14π electron aromatic system, 1,3,5,7-tetrathia-2,4,6,8-tetraazaazulene 13 in which all the S 4 N 4 atoms have been retained [12]. Reaction of phenyl vinyl sulphone and S 4 N 4 indeed gave the same compound 13, but in very low yield (4%).…”

Section: Methodsmentioning

confidence: 95%

Poly-sulfur-nitrogen heterocycles via sulfur chlorides and nitrogen reagents

Torroba

1999

J. prakt. Chem.

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Nitrogen and sulfur organic aromatic heterocycles are formally derived from aromatic carbon cycles by a heteroatom taking the place of a ring carbon atom or a complete CH=CH group. The presence of heteroatoms results in significant changes in the cyclic molecular structure due to the availability of unshared pairs of electrons and the difference in electronegativity between heteroatoms and carbon. Therefore, nitrogen and sulfur heterocyclic compounds display physicochemical characteristics and reactivity far from the parent aromatic hydrocarbons. On the other hand, the presence of many nitrogen and sulfur atoms in a ring is normally associated with instability and difficulties in the synthesis but, in fact, surprisingly stable heterocycles with unusual properties can be frequently obtained from simple or- Poly-Sulfur-Nitrogen Heterocycles via Sulfur Chlorides and Nitrogen ReagentsTomás Torroba* Burgos/Spain, Departamento de Química, Facultad de Ciencias, Universidad Received October 28th, 1998, respectively January 4th, 1999Keywords: Conducting materials, Nitrogen heterocycles, Phosphorus heterocycles, Selenium, Sulfur heterocycles Abstract: The family of poly-sulfur-nitrogen heterocycles includes highly stable aromatic compounds that display physicochemical properties with relevance in the design of new materials, especially those relating to molecular conductors and magnets. The interesting characteristics found in many of these heterocycles have led to the development of modern synthetic methods that are the subject of this review. Heterocycles such as 1,2,3-and 1,2,5-thiadiazoles, 1,2,3-and 1,3,2-dithiazoles, 1,2,3,5-dithiadiazoles, thiatriazines, trithiadiganic substrates and the appropriate inorganic reagent. This paper reviews the most common synthetic methods to obtain poly-sulfur-nitrogen heterocyclic systems that lie in the middle way between organic and inorganic chemistry. Carbon atoms confer high stability to such rings, according to the aromaticity and antiaromaticity rules, and the nitrogen-sulfur core gives unusual properties to the compounds, in accordance with their electron rich π-excessive nature. The physicochemical properties of this family of compounds have relevance in the design of new materials, specially concerning organic conductors. In contrast with the number and variety of such heterocycles, the number of synthetic methods to afford them is, in practice, restricted to the availability of the appropriate sulfur reagent. The classification of synthetic methods follows the applications of the most common sulfur reagents to the synthesis of heteroaromatic carbon-nitrogen-sulfur rings and sometimes extends to selenium or phosphorus related heterocycles. Binary inorganic sulfur-nitrogen cycles are covered by some reports from Chivers and Oakley [1]. Some binary S-N rings, as B-F in figure 1, constitute the models and sometimes precursors of the organic members of the series.azines, dithia(and trithia)diazepines, trithiatriazepines, dithia(and trithia)tetrazozines, and fused systems are mo...

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“…reacts with phenyl vinyl sulfoxide, an effective equivalent of acetylenes in some addition reactions, with the formation of the new 14π-electron aromatic system 1,3,5,7-tetrathia-2,4,6,8-tetraazaazulene (58)[42,43]. A possible mechanism for the transformation of S 4 N 4 into the product 58 includes 1,3-dipolar cycloaddition of the alkene at the S(1)-S(3) bond, leading to the intermediate 59; subsequent thermal elimination of phenylsulfenic acid leads to the bicyclic structure 60, in which the S 4 N 4 fragment is opened as a result of an electrocyclic process with the formation of the tricyclic structure 61.…”

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confidence: 99%