Synthese homokonjugierter Polyene: 2,4-Dimethylenbicyclo[3.2.0]oct-6-en und 2,5-Dimethylenbicyclo[4.2.0]non-7-en

The synthesis of the two homoconjugated trienes has been achieved by cleavage of the strained -bonds of suitable cyclopropane and cyclobutane precursors. Ionization energies are discussed.

     

Synthesis und thermisches Verhalten von exo-3-Methylidentricyclo[3.2.1.02,4]oct-6-en

Synthesis and Thermal Behaviour of exo-3-Methylidenetricyclo[3.2.1.0^2,4]oct-6-ene The title compound 3 has been prepared in 16% yield starting from 8,9,10-trinorborna-2,5-diene. Heating 3 at 140° for 4 h does not give triafulvene and cyclopentadiene by Diels-Alder cycloreversion, instead the tetracyclic compound 10 has been isolated (81%), which is presumably formed via the diradical 11.     

Thermal reactions of 7-d- and 8-d-bicyclo[4.2.0]oct-2-enes

The gas phase thermal reactions exhibited by bicyclo[4.2.0]oct-2-ene and 7-d and 8-d analogues at 300 degrees C have been followed kinetically through GC and 2H NMR spectroscopic analyses. In contrast to the pattern of transformations exhibited by bicyclo[3.2.0]hept-2-ene and deuterium-labeled analogues, no reactions initiated by C1-C6 bond cleavage are seen, epimerization at C8 is much faster than [1,3] shifts leading to bicyclo[2.2.2]oct-2-ene, and the ratio of rate constants for [1,3] carbon migration with inversion versus migration with retention is approximately 1.4. Homolysis of C1-C8 to give a conformationally flexible diradical intermediate having a relatively long lifetime and multiple options for further reaction (re-formation of C1-C8 with or without net epimerization, fragmentation to 1,3-cyclohexadiene and ethylene, migration to the original C3 with inversion or retention) accords well with the observations. Clearly, orbital symmetry control does not govern stereochemistry for the [1,3] sigmatropic carbon shifts.     

Thermal chemistry of bicyclo[4.2.0]oct-2-enes

At 300 degrees C, bicyclo[4.2.0]oct-2-ene (1) isomerizes to bicyclo[2.2.2]oct-2-ene (2) via a formal [1,3] sigmatropic carbon migration. Deuterium labels at C7 and C8 were employed to probe for two-centered stereomutation resulting from C1-C6 cleavage and for one-centered stereomutation resulting from C1-C8 cleavage, respectively. In addition, deuterium labeling allowed for the elucidation of the stereochemical preference of the [1,3] migration of 1 to 2. The two possible [1,3] carbon shift outcomes reflect a slight preference for migration with inversion rather than retention of stereochemistry; the si/sr product ratio is approximately 1.4. One-centered stereomutation is the dominant process in the thermal manifold of 1, with lesser amounts of fragmentation and [1,3] carbon migration processes being observed. All of these observations are consistent with a long-lived, conformationally promiscuous diradical intermediate.     

Synthesen und einige thermische und strukturelle Eigenschaften von Hydraziniumfluorotitanaten(IV)

Zusammenfassung Die Synthesen von [N₂H₅]₂TiF₆, [N₂H₅]₂TiF₆ · 2 HF und N₂H₆TiF₆ sind beschrieben, die thermischen Eigenschaften, die Infrarotspektren werden diskutiert. Eine Disproportionierung von Hydrazin in Stickstoff und Ammoniak wurde festgestellt. Die Zuordnung der Infrarotbanden (4000–250 cm^–1) deutet bei den ersten zwei Verbindungen auf die Hydrazinium¹⁺-Verbindungen hin.

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The synthesis and some thermal and structural properties of hydrazinium fluorotitanates(IV)

The synthesis of [N₂H₅]₂TiF₆, [N₂H₅]₂TiF₆ · 2 HF and N₂H₆TiF₆ is described. The thermal properties and infrared spectra of the obtained compounds are discussed. Disproportionation of hydrazinium into nitrogen and ammonia is observed. The assignation of the bands in infrared spectra [4000 to 250 cm^–1] of the first two compounds is consistent with the presence of hydrazinium¹⁺ ion.

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Mit 2 Abbildungen     

Herstellung der reinen,bicyclischen Olefine Bicyclo[4.2.1]non-2-en,Bicyclo[4.2.1]non-3-en und Bicyclo[4.2.1]non-7-en

Synthesis of the pure, bicyclic olefines Bicyclo[4.2.1]non-2-ene, Bicyclo[4.2.1]non-3-ene and Bicyclo[4.2.1]non-7-ene The synthesis of the olefines bicyclo[4.2.1]non-2-ene ( 3 ), bicyclo[4.2.1]non-3-ene ( 4 ) and bicyclo[4.2.1]non-7-ene ( 5 ) of high ‘certified’ purity from one common precursor ( 7 ) is described.     

Sauerstoff-insertion bei der umlagerung von 2-aza-bicyclo[2.2.1]hept-2-enderivaten

N-Acyclation of N-hydroxy-2-azabicyclo[2.2.1]hept-2-ene causes rearrangement to oxa-aza-bicycles ($\text{7}$, $\text{8}$) by insertion of the hydroxalamine oxygen into the heterocyclic system. The mechanism is elucidated.     

Conformational analysis in the reversible intramolecular [2+2] photocycloaddition of diphenylbicyclo[4.2.0]oct-3-ene-2,5-diones

An irradiation of diphenylbicyclo[4.2.0]oct-3-ene-2,5-diones bearing variously substituted Me groups resulted in the reversible intramolecular [2+2] cycloaddition between the excited enedione CC double bond and the facing endo-phenyl ring to exclusively give pentacyclotetradeca-10,12-diene-2,7-diones. The equilibrated product ratios were much dependent on the substitution pattern of the Me-groups as well as the irradiated wavelength. The regiochemistry of these photoadditions was elucidated on the basis of the restricted conformation of the starting enediones.     

Thermal disrotatory electrocyclic isomerization of cis-bicyclo[4.2.0]oct-7-ene to cis,cis-1,3-cyclooctadiene

[reaction: see text] The ratio of observed rate constants, k/k', for thermal isomerizations of cis-bicyclo[4.2.0]oct-7-ene and its 2,2,5,5-d(4) analogue to cis,cis-1,3-cyclooctadienes at 250 degrees C is 1.17, indicative of a secondary, not a primary, deuterium kinetic isotope effect. The reaction does not occur through a [1,5] hydrogen shift from the transient cis,trans-1,3-cyclooctadiene intermediate to form the observed cis,cis-diene product.     

Gold-catalyzed tandem 1,3-migration/[2 + 2] cycloaddition of 1,7-enyne benzoates to azabicyclo[4.2.0]oct-5-enes

A synthetic method that relies on gold(I)-catalyzed tandem 1,3-migration/[2 + 2] cycloaddition of 1,7-enyne benzoates to prepare azabicyclo[4.2.0]oct-5-enes is described.