Synthesis and Some Reactions of 2,4,6‐Cycloheptatrienethione

Dugger, Harry A.; Dreiding, Aǹdré S.

doi:10.1002/hlca.19760590305

Cited by 17 publications

(4 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…6.68 ( d x d , H-C(4')) and at 6.55 (d, H-C(3')) remained unchanged. We conclude that the NOE-enhancement is on H-C (4) Deuterio-2-diisopropylamino -6-(3', 4: 6'-trideuterio-2'-diisopropylaminodropon -T-y1)-3, 7-dehydrotropone ([2H4]-5). A similar experiment to the preceding one using CF3COOD gave [2H4]-5, m.p.…”

Section: -Diisopropylumino-6-(2'-diisopropyiaminotropon-7'-yl)-3 7-mentioning

confidence: 99%

“…These shifts and the increase in intensities have their analogy in the comparison of tropothione and two of its derivatives with tropone and the corresponding derivatives (A]. = 46 to 70 nm), a comparison which has been summarized in [4].…”

mentioning

confidence: 96%

“…2-Diisopropylamino-3,7-dehydrotropothione (2)3). -Treatment of 2-diisopropylamino-3,7-dehydrotropone (1) [ 1 J with phosphorus pentasulfide and triethylamine at room temperature in dichloromethane (compare [4]) for 9 days caused simple replacement of the 0-by a S-atom to yield 2-diisopropylamino-3,7dehydrotropothione (2) as an orange solid, m.p. 105-106".…”

mentioning

confidence: 99%

See 2 more Smart Citations

ChemInform Abstract: REACTIONS OF 2‐DIISOPROPYLAMINO‐3,7‐DEHYDROTROPONE: CONVERSION TO THE THIONE AND DIMERIZATION

Gray¹,

Dreiding²

1982

Chemischer Informationsdienst

View full text Add to dashboard Cite

~ ~ ~~Reaktionen von 2-Diisopropylamino-3,7-dehydrotropon: Umwandlung in das Thion und Dimerisierung Zusammenfassung Behandlung von 2-Diisopropylamino-3,7-dehydrotropon (1) mit Phosphorpentasulfid ergab 2-Diisopropylamino-3,7-dehydrotropothion (2). Mit Trifluoressigsaure entstand aus 1 ein stabiles Dimeres (5), das ein Dehydrotropon-sowie ein Tropon-Ringsystem enthalt. Die Strukturen von 2 und 5 ergeben sich aus ihren Spektraleigenschaften.In continuance of our studies on the dehydrotropone system [l-31, we examined the behaviour of 2-diisopropylamino-3,7-dehydrotropone ( 1)2) under two conditions: 1) with phosphorus pentasulfide, which led to the first example of a 3,7-dehydrotropothione, and 2) with trifluoroacetic acid, which induced a dimerization involving an unusual 3,7-dehydrotropone 4 tropone ring opening.1. 2-Diisopropylamino-3,7-dehydrotropothione (2)3). -Treatment of 2-diisopropylamino-3,7-dehydrotropone (1) [ 1 J with phosphorus pentasulfide and triethylamine at room temperature in dichloromethane (compare [4]) for 9 days caused simple replacement of the 0-by a S-atom to yield 2-diisopropylamino-3,7-dehydrotropothione (2) as an orange solid, m.p. 105-106". Its spectral properties, shown in Table 1 together with those of 1, offer structural confirmation as follows: I )In accordance with the previous literature [l-41, we prefer to use the dehydrotropone and the tropone nomenclature throughout this paper, rather than the systematic nomenclature, which is given in footnotes 2. 3 and 5. The systematic name for 1 is 7-diisopropylamino-bicyclo[3.2.0]-1(7),2,4-heptatrien-6-one. The systematic name for 2 is 7-diisopropylamino-bicyclo[3.2.0]-I (7).2,4-heptatriene-6-thione.

show abstract

Section: -Diisopropylumino-6-(2'-diisopropyiaminotropon-7'-yl)-3 7-mentioning

confidence: 99%

mentioning

confidence: 96%

See 1 more Smart Citation

ChemInform Abstract: REACTIONS OF 2‐DIISOPROPYLAMINO‐3,7‐DEHYDROTROPONE: CONVERSION TO THE THIONE AND DIMERIZATION

Gray¹,

Dreiding²

1982

Chemischer Informationsdienst

View full text Add to dashboard Cite

show abstract

“…The chemical and physical properties of the three-, five-, and seven-membered cyclic conjugated ketones and thioketones have been the subject of numerous experimental [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] and theoretical studies. [31][32][33][34][35] In particular, the ''nonbenzoid aromatic character'' of the three-and seven-membered ring systems and the ''anti-aromatic character'' of the fivemembered ring systems, as well as their high reactivity, have attracted a great deal of attention.…”

Section: Introductionmentioning

confidence: 99%

Static electric properties of conjugated cyclic ketones and thioketones

Eckart¹,

Fülscher²,

Serrano‐Andrés³

et al. 2000

The Journal of Chemical Physics

View full text Add to dashboard Cite

Articles you may be interested inHow large is the static electric (hyper)polarizability anisotropy in HXeI?The results of ab initio calculations of static electric properties of a series of cyclic conjugated ketones and thioketones are presented. Dipole moments, dipole polarizabilities, as well as the first and second hyperpolarizabilities, were evaluated at different levels of theory: SCF, CASSCF, MP2, CCSD, CCSD͑T͒, and CASPT2 methods were used. Both MP2 and CASPT2 methods have been shown to perform well in the calculation of such properties. The dependence of the electric properties on the extent of the -electron conjugation and on the replacement of the keto by the thioketo group is analyzed. Cyclic conjugated thioketones are shown to exhibit significant nonlinear electric properties which make them prospective building blocks for nonlinear optical materials.

show abstract

Cyclopentadienylidene, XV. Cyclohepta[c]pyrrol‐6(2H)‐thion, ein stabiles Tropothion

et al. 1979

View full text Add to dashboard Cite

Cyclohepta[c]pyrrol-6(2H)-one (2) lassen sich nach zwei Methoden in stabile Thioanaloge 5 iiberfiihren, die chemisch als Methoiodide 6 und durch Reaktion mit 9-Diazo-1,8-diazafluoren (8) bzw. Diphenyldiazomethan (11) charakterisiert werden konnen. Dipolmomente von 2 und 5 werden mitgeteilt, spektroskopische Daten von 5 und deren Folgeprodukte diskutiert. Cyclopentadienylidenes, XV') Cyclohepta[e]pyrrole-6(2 H )-thione, a Stable TropothioneCyclohepta[c]pyrrole-6(2H)-thiones (5) are synthesized in two ways from cyclohepta[c]pyrrole-6(2H)-ones (2). The thiones are characterized by reaction with methyl iodide, 9-diazo-I ,I-diazafluorene (8), and diphenyldiazomethane (ll), respectively. Dipole moments of 2 and 5 are reported, spectroscopic data of 5 and of some reaction products are discussed, 2,4,6-Cycloheptatrien-l -thion (l)'), das Schwefelanalogon des Tropons, ist in verdunnter Losung spektroskopisch sicher nachzuweisen und intermediar via Cycloadditi~nsreaktionen~") abzufangen, jedoch als Reinsubstanz nicht i~o l i e r b a r~~) .Wir fanden, daB im Gegensatz zu 1 Cyclohepta[c]pyrrol-6(2 H)-thione 5 bei Raumtemperatur durchaus stabile und gut handhabbare Verbindungen darstellen und berichten hier uber Synthesewege, spektroskopische Eigenschaften und einige chemische Reaktionen von 5.Als Edukt zur Synthese von 5a benutzten wir das Cyclohepta[c]pyrrol-6(2H)-on 2a4), das mit Thionylchlorid nach der Schonbergschen Methode') glatt in das Dichlorid 3 a 4 a uberfuhrbar ist. Analytisch charakterisiert wurde das stabilere Perchlorat 4ap. Mit frisch bereiteter waBriger Natriumsulfidlosung laBt sich 3 a + 4a mit nahezu quantitativer Ausbeute in 5a umwandeln, das in Form dunkelroter Kristalle isoliert werden kann. Daneben laBt sich 5a auch nach der Phosphor(V)-sulfid-Methode6' direkt aus 2 a gewinnen, wenn man in Dimethylglycol als Losungsmittel arbeitet und

show abstract

Synthesis and Some Reactions of 2,4,6‐Cycloheptatrienethione

Cited by 17 publications

References 13 publications

ChemInform Abstract: REACTIONS OF 2‐DIISOPROPYLAMINO‐3,7‐DEHYDROTROPONE: CONVERSION TO THE THIONE AND DIMERIZATION

ChemInform Abstract: REACTIONS OF 2‐DIISOPROPYLAMINO‐3,7‐DEHYDROTROPONE: CONVERSION TO THE THIONE AND DIMERIZATION

Static electric properties of conjugated cyclic ketones and thioketones

Cyclopentadienylidene, XV. Cyclohepta[c]pyrrol‐6(2H)‐thion, ein stabiles Tropothion

Contact Info

Product

Resources

About