Tricyclo[4.3.1.0<sup>1,6</sup>]deca‐2,4,7‐trien, ein acider alicyclischer Kohlenwasserstoff

Grimme, Wolfram; Kaufhold, Marcel; Dettmeier, U.; Vogel, Emanuel

doi:10.1002/ange.19660781211

Cited by 20 publications

(4 citation statements)

References 7 publications

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“…(60) and (62) give similar dimers when heated (192,1931. According to the Woodward-Hoffmann rule, a 6 + 6 addition cannot take place directly [1941, but must proceed in several steps. This is confirmed by the fact that a 4 + 6 addition product (69) has been found as an intermediate [1921. Like cycloheptatriene (Section IIIc) and 2,7-dimethyloxepin 11901, (60) is converted by exposure to light into the valence-isomeric 2-azabicyclo[3.2.0]heptadiene derivative (70), which in turn is reconverted into (60) by heating "901.…”

Section: Systems Containingmentioning

confidence: 87%

The Norcaradiene Problem

Maier

1967

Angew. Chem. Int. Ed. Engl.

181

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Dedicated to Professor R. Criegee on the occasion of his 65th birthdayCompounds having the norcaradiene structure are stable if one of the double bonds of the norcaradiene also belongs to a benzene ring or if C atoms I and 6 are fixed in position by a bridge. A similar effect that favors the norcaradiene form is produced by the incorporation of nitrogen atoms in positions 3 and 4. Cycloheptatriene and most of the simply substituted tropilidenes exist exclusively in the monocyclic triene form. It has been possible in some cases to detect a valence-tautorneric equilibrium between the norcaradiene and the cycloheptatriene ring system. Non-classical stabilization of compounds having norcaradiene or cycloheptatriene structure in the sense of a pseudoaromatic "homobenzene" is only very slight, if it occurs at all.

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Section: Systems Containingmentioning

confidence: 87%

The Norcaradiene Problem

Maier

1967

Angew. Chem. Int. Ed. Engl.

181

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“…Pentane was added dropwise to a concentrated benzene solution until crystals begin to separate. After a few hours, the crystalline material was filtered and dried in vacuo to give 140 mg of yellow crystals (68%); mp 203-205 °C; NMR (CDCL) 6.75-7.60 (8 H, m), 3 Hydrolysis of Amino Ester 3, = H. Amino ester 3, = H (245 mg, 0.62 mmol) was dissolved in 20 ml of hot 4 N KOH and refluxed in an oil bath. After 5 h the mixture was allowed to cool, whereby the oily droplets which had formed solidified.…”

Section: Methodsmentioning

confidence: 99%

A 10-.pi.-electron heterocycle: 2,3,4-tricarbomethoxy-6,7,8,9-dibenzo-1,5-diazonine

Farnum¹,

Rasheed²

1977

J. Org. Chem.

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“…The solid formed was ffltered and washed w i t h a 1:l mixture of chlorofodhexane to give 2.7-dioxa-5. 10-diaza[4.4.4]propellane7 (1) in 73% yield. In the case of 2 a solution of 1.2-cyclohexanedione (8.9 mmol) and 0-aminophenol(l7.8 mmol) in ethanol (30 ml) was refluxed for 2h.…”

Section: One Step Syntheses Of Heteropropellanesmentioning

confidence: 98%

One Step Syntheses of Heteropropellanes

Ortíz¹,

Carrasco²,

Höpfl³

et al. 1998

Synthetic Communications

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The preparation of two new propellanes containing the oxazino-oxazine moiety is described. The structure of 2,7-dioxa-5,1O-diaza[4.4.4] propellane was determined by X-ray crystallographic analysisThe formation of tricyclic compounds joined by a carboncarbon single bond has been of great synthetic interest. Propellanes w i t h three or four membered ring systems can be synthesized by the reaction of indan-Zone with carbenes,l photochemical m g e m e n t of b,yunsaturated cyclic ketones2 or by photochemical cycloaddition of 1,2-dichloro-ethylene to bicyclo[3.3.0]oct-5-en-2-one.3 In the case of propellanes containing five-or six-membered rings, various synthetic methods have been described.4 These propellanes show interesting stereoelectronic effects, specially the 2,5,7,10,11,14-hexaoxa-[4.4.4]pr0pellane.~ During our study of condensation reactions between aminoalcohols and adicarbonyl compounds, different structure types including mono-, bi-and tricyclic 1294 ORTfZ ET AL. ring systems have been obtained.6 Herein we describe the formation of the new heternpropellanes 1 and 2 by condensation of erhanolamine or o-aminophenol with 1.2-cyclohexanedione (scheme 1). 11 11 8 18 19 14 14 1 2 Scheme 1The I.eaction between the aminoalcohols and 1.2-cyclohexanedione was carried out under the following conditions: ethanolamine (17.8 mmol) was added dropwise to a solution of cyclohexanedione (8.92 mmol) in ethyl acetate (60 ml) and the mixture was refluxed for 7h. The solid formed was ffltered and washed w i t h a 1:l mixture of chlorofodhexane to give 2.7-dioxa-5. 10-diaza[4.4.4]propellane7 (1) in 73% yield. In the case of 2 a solution of 1.2-cyclohexanedione (8.9 mmol) and 0-aminophenol(l7.8 mmol) in ethanol (30 ml) was refluxed for 2h. The solid formed was filtered and washed with ethyl acetate to give (3,4,8,9)-dibenzo-2,7-dioxa-5,10-diaza[4.4.4]propellane~ (2) in 60% yield. 3 4 Fig. 1 Downloaded by [Tulane University] at 02:45 28 September 2014 HETEROPROPELLANES 1295 ci2 N10 Fig. 2 Molecular structure of compound 1The molecular ion at m/z =198 from mass spectromeuy could be amibuted to the structure types 1,3 or 4. Smcture 3 can be excluded based on the 13C NMR data which show only one signal at S = 84.0 ppm for the C-1 and C-6 carbons.However, spectroscopic methods do not allow an easy distinction between 1 and 4. Therefore the propellane type struchlre of compound 4 was determined by Xray crystallographic andysisg. The molecule is located on a special position in the crystal lattice showing C2 symmetry and consists of three fused six-membered rings in a chair-like conformation as shown in Fig. 2 . Additionally a stabilizing anomeric effect from the nitrogen atoms can be observed. Due to the presence of stereoelectrunic effects, the Cl-N10 bond length (1.431(4)& is significantly shorter than C4-NlO (1.463(4)h. Furthermore, the 02-Cl bond length (1.455(3)& is longer than 0 2 x 3 (1.432(4) A). From these observations it may be concluded that the predominant factor in the formation of compound 1 over 4 is the presence of ...

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Tricyclo[4.3.1.0^1,6]deca‐2,4,7‐trien, ein acider alicyclischer Kohlenwasserstoff

Cited by 20 publications

References 7 publications

The Norcaradiene Problem

The Norcaradiene Problem

A 10-.pi.-electron heterocycle: 2,3,4-tricarbomethoxy-6,7,8,9-dibenzo-1,5-diazonine

One Step Syntheses of Heteropropellanes

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Tricyclo[4.3.1.01,6]deca‐2,4,7‐trien, ein acider alicyclischer Kohlenwasserstoff

Cited by 20 publications

References 7 publications

The Norcaradiene Problem

The Norcaradiene Problem

A 10-.pi.-electron heterocycle: 2,3,4-tricarbomethoxy-6,7,8,9-dibenzo-1,5-diazonine

One Step Syntheses of Heteropropellanes

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Tricyclo[4.3.1.0^1,6]deca‐2,4,7‐trien, ein acider alicyclischer Kohlenwasserstoff