Neue 1,6-Methano[10]annulen-Derivate durch Umlagerungsreaktionen der Trimethylsilyl-Gruppe

New Derivatives of 1,6-Methano[10]annulene by Rearrangement of Trimethylsilyl Groups Oxidation of derivatives of trimethylsilyl-substituted bicyclo[4.4.1]undeca-1,3,5,7-tetraenes 1–3 leads to 1,6-methano[10]annulenes. In the case of 2 and 3a , rearrangement of the trimethylsilyl group takes place. This rearrangement can be used to prepare 2,9-disubstituted 1,6-methano[10]annulenes.     

Synthesen und chemische Eigenschaften neuer «Donor-Akzeptor»-stabilisierter Molekülsysteme mit zentraler Bicyclo [4.4.1]undeca-l (10), 3,6,8-tetraen-2,5-diyliden-Gruppe

Syntheses and Chemical Properties of New ‘Donor-Acceptor’-stahilized Molecular Systems with a Central Bicyclo[4.4.1] undeca-l(10).3,6,8-tetraene-2,5-diylidenc Group The synthesis of X-methyl-2-(5-oxobicyclo[4.4.1]undeca-l)10(,3,6,8-tetraen-2-yliden)-l,3-benzodithiol ( 4 ) is described starting with the keto-enol mixture 2 and 5-methyl-1,3-benzodithiolium perchlorate. Under rearomatization of the central frame protonation of 4 yields the salt 4c. The reaction of 4 with dicyanoketene gives the ‘push-pull-substituted’ 5 , and with 9-carbonylfluorene the fulvalene derivative 7 , which can be protonated by CF₃CO₂H at C(9″) to the salt 8. The reaction of 2-methylthio-l,3-dithiolium jodide 9 with the keto-enol mixture 2 yields 10 , which, on protonation at the carbonyl group by CF₃CO₂H, gives the salt 11 under rearomatization. The spectral data of the new compounds 4, 4c, 5, 7, 8, 10 and 11 are reported and discussed.     

A new route to [3.5.3] armilenium ion

Treatment of bicyclo[4.4.1]undeca-2,4,7,9-tetraen-11-ol with FSO₃H-SO₂-CH₂Cl₂, at ?70° resulted in the formation of [3.5.3]armilenium ion. The general pathway to the ion is proposed.     

(4-溴甲基双环[4.4.1]-1,3,5,7,9-十一碳五烯基-3-)甲醇环氧化反应机理的理论研究

A reaction mechanism of epoxidation reaction of the 4-(bromomethyl)bicyclo4.4.1undeca-1,3,5,7,9-pentaen-3-ylmethanol has been studied by using the density functional theory(DFT) method at B3LYP level with 6 31G* basis set. The geometric structures of reactant, product and transition state have been optimized. The transition state is found by the QST2 method and characterized by the vibration frequency analysis. The intrinsic reaction coordinate(IRC) for this reaction is traced and confirms the reaction mechanism. The changes and the nature of related chemical bonds along the IRC path have been analyzed by the theory of electronic charge density. The result shows that the elimination reaction and ring closing reaction are synergistic, and the hydrogen in the elimination reaction derives from hydroxyl. In addition, the activation energy of the reaction is 139.2 kJ/mol.     

A novel bicyclic system, 1,6-diaza-3,8-dioxabicyclo[4.4.1]undecane

Condensation of monoethanolamine with formaldehyde affords 1,6-diaza-3,8-dioxabicyclo[4.4.1]undecane andN,N-methylene-bis(oxazolidine) in a ratio of 18.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 342–343, February, 1994.     

Electrostatic Defromation Properties in the Crystal Structure of Tricyclo[4.4.1.01,6]undeca-2,4,7,9-tetraene-11,11-dicarbonitrile

The deformation density and potential have been determined in molecular crystals of tricyclo[4.4.1.0^1,6]ndeca-2,4,7,9-tetraene-11,11-dicarbonitrile at 150 K from X-ray diffraction measurements. A significant degformation density peak is found near the mid-poind of the the transannular bond. The four short bonds in the annuelene ring acquire slightly more residual density compared to the other bonds, confirming the bisnorcaradienic character of the molecule. Similar trends are noted in the deformation electrostatic potential maps.     

[4 + 6]-cycloaddition von 1,3-butadien an hexacarbonyl-μ-η6:6-heptafulvalen-dichrom(0)

The thermal reaction of heptafulvalene (I) with [Cr(CO)₃(CH₃CH)₃] (II) gives the hexacarbonyl-η^6:6-heptafulvalenedichromium(0) complex (III). UV irradiation of complex III in THF solution, with 1,3-butadiene (IV) in successive [4 + 6]-cycloadditions and decomplexations gives the complexes tricarbonyl-η⁶-11-(2,4,6-cycloheptatrien-1-ylidene)bicyclo[4.4.1]undeca-2,4,8-trine-chromium(0) (V) and tricarbonyl-η⁶-bi(bicyclo[4.4.1]undeca-2,4,8-trien-11-ylidene)-chromium(0) (VI). On warming, VI looses the bi(bicyclo[4.4.1]undeca-2,4,8-trien-11-ylidene) hydrocarbon ligand (VII). The reaction of VII with [Mo(CO)₃(diglyme)] (VIII) gives the tricarbonyl-η⁶-bi(bicyclo[4.4.1]undeca-2,4,8-trien-11-ylidene)molybdenum(0) complex (IX). The compounds III, V–VII and IX were characterized by IR and NMR spectra (¹H, ¹³C) and by C,H elemental analysis.     

Structural isomer differentiation of 1,6-diaza-3,8-dioxabicyclo[4.4.1]undecane and N,N'-methylenebis(oxazolidine) by mass spectrometry

The title compound types are structural isomers. The absence of literature studies dealing with the mass spectrometric gas-phase behavior of such compounds prompted a search for the best conditions for differentiation between the two prototype examples (R,R)-5,10-diphenyl-1,6-diaza-3,8-dioxabi-cyclo[4.4.1]undecane and N,N'-methylenebis[(R)-4-phenyloxazolidine]. Attempts to differentiate between the isomers by NMR were inconclusive and X-ray crystallography had to be used. The best mass spectrometric results were obtained using gas-phase ionization techniques, particularly chemical ionization, whereby protonated molecules were observed. The fragmentation pathways were elucidated from MS/MS studies and from experiments performed on hexadeuterated samples of each compound.     

Photochemische reaktionen von übergansmetall-olefinkomplexen: III. [4 + 6]-cycloaddition konjugierter diene an hexacarbonyl-μ-η6:6(-1,1′-bi(2,4,6-cycloheptatrien-1-yl)dichrom(O)

UV irradiation of hexacarbonyl-μ-η^6:6-1,1′-bi(2,4,6-cycloheptatrien-1-yl)dichromium(O) (I) in THF in the presence of 1,3-butadiene (A), E-1,3-pentadiene (B) and EE-2,4-hexadiene (C) causes preferentially a twofold [4 + 6]-cycloaddition and formation of the hexacarbonyl-μ-2–5 : 8.9-η-2′–5′ : 8′,9′-η-11,11′-bi(bicyclo-[4.4.1]undeca-2,4,8-trien-11-yl)dichromium(O) complexes (IVA–IVC). Partial decomplexation after the first [4 + 6]-cycloaddition yields isomeric tricarbonyl-2–5:8,9-η- (IIA–IIC) and tricarbonyl-2′–7′-η-{11-(2′,4′,6′-cycloheptatrien-1′-yl)bicyclo[4.4.1]undeca-2,4,8-triene}chromium(O) complexes (IIIA–IIIC). With 2,3-dimethyl-1,3-butadiene (D) mainly dicarbonyl-2–6 : 2′–4′-η-{1-(2′,3′-dimethyl-3′-buten-1′,2′-diyl)-7-(8″,9″-dimethylbicyclo[4.4.1]undeca-2″, 4″,8″-trien-11″-yl)cyclohepta-3,5-dien-2-yl}chromium(O) (VD) besides small amounts of pentacarbonyl-μ-2–6 : 2′–4′-η-2″–7″-η-{1-(2′,3′-dimethyl-3′-buten-1′,2′-diyl)-7-(2″, 4″,6″-cycloheptatrien-1″-yl)cyclohepta-3,5-dien-2-yl}dichromium(O) (VID) and tricarbonyl-2′-7′-η-{11-(2′,4′,6′-cycloheptatrien-1′-yl)-8,9-dimethyl-bicyclo[4.4.1]undeca-2,4,8-triene}-chromium(O) (IIID) is obtained. VD adds readily CO to yield tricarbonyl-2–5 : 8,9-η-11,11′-bi(8,9-dimethyl-bicyclo[4.4.1]undeca-2,4,8-trien-11-yl)chromium(O) (VIID). Finally D adds to VID under formation of pentacarbonyl-μ-2–6 : 2′–4′-η-2″–5″ : 8″,9″-η-{1-(2′,3′-dimethyl-3′-buten-1′,2′-diyl)-7-(8″,9″-dimethyl-bicyclo[4.4.1]- undeca-2″,4″,8″-trien-11″-yl)cyclohepta-3,5-dien-2-yl}dichromium(O) (VIIID). From IVA–IVC the hydrocarbon ligands (IXA–IXC) can be liberated by P(OCH₃)₃ in good yields. The structures of the compounds IIA–IXC were determined by IR     

Synthesis and Dimerization of Bicyclo [4.4.1] undec-1 (11)-ene,a Bridged trans-Cycloheptene

The synthesis of bicyclo [4.4.1] undec-1 (11)-ene ( 5 ) by intramolecular Wittig reaction is described. The Bredt olefin could not be isolated, but dimerized rapidly to a novel compound 15 containing a cyclopropane ring. The olefin 5 was trapped in situ by 2,5-diphenylbenzo [c]furan.     

Spirocyclohexadienones: VIII. 1-R-3,3-Dimethyl-2-azaspiro[5.5]undeca-1,7,10-trien-9-ones

1-R-3,3-Dimethyl-2-azaspiro[5.5]undeca-1,7,10-trien-9-ones were synthesized by condensation of 4-(p-methoxyphenyl)-2-methylbutan-2-ol with nitriles RCN in the presence of a concn. sulfuric acid.     

Synthesis of Methyl 3,6-Dioxo-endo-tricyclo[6.2.1.02,7]undeca- 4,9-diene-2-carboxylate as Synthetic Intermediate for Conduritol Derivatives

Gentisic acid reacted with methyl iodide in HMPA to give 94% of the corresponding methyl ester. Its oxidation with Ag₂O in toluene afforded 57% of methoxycarbonylbenzoquinone as yellow crystals. Reaction of the latter with cyclopentadiene resulted in formation of methyl 3,6-dioxotricyclo[6.2.1.02,7]undeca-4,9-diene-2-carboxylate (21%).     

Spirocyclohexadienones: XII. Dienone-phenol rearrangement of 1-substituted 2-azaspiro[4.5]undeca-1,6,9-trienes and their analogs

Hydrolytic cleavage of 1-substituted 2-azaspiro[4.5]undeca-1,6,9-trienes in acid medium is accompanied by dienone-phenole rearrangement with formation of substituted N-[2-(p-hydroxyphenyl)ethyl] carboxylic acid amides. 1,2-Dimethoxy-3-oxo-15-phenyl-14-azadispiro[5.1.5.2]pentadeca-1,4,14-triene and 2′-R-7a′-methyl-3a′,4′,5′,6′,7′,7a′-hexahydrospiro[cyclohexa[2,5]diene-1,3′-indol]-4-ones undergo analogous cleavage.     

A Regiospecific Photochemical Rearrangement of 2-Azabenzotricyclo[5.2.2.01,5]- to 2-Azabenzotricyclo[6.2.1.01,5]undecatrienone

The 2-azatricyclo[5.2.2.0^1,5]undeca-4,8,10-trien-3-ones 1a and 1b gave on irradiation the 2-azatricyclo-[6.2.1.0^1,5]undeca-4,6,9-trien-3-ones 2a and 2b , respectively. The rearrangement was found to be solvent-, oxygen-, and wavelength-independant.     

Photochemische reaktionen von übergangsmetall-olefin-komplexen: XI. [4+ 6]-cycloaddition von tricyclo[6.3.0.02,7]undeca-3,5-dien antricarbonyl-η6-1,3,5-cycloheptatrien-chrom(0)

The photochemical reaction of tricarbonyl-η⁶-1,3,5-cycloheptatriene-chromium(0) (I) with tricyclo[6.3.0.0^2,7]undeca-3,5-diene (II) in n-pentane at 248 K yields the [4 + 6]-cycloadduct tricarbonyl-η⁶-pentacyclo[7.6.2.1^10,15.0^2,8.0^3,7]octadeca-11,13,16-triene-chromium(0) (III). Detachment of the pentacyclic triene ligand from chromium can be achieved with trimethylphosphite. The constitutions of complex III and of the pentacyclic hydrocarbon IV were determined by spectroscopic means.     

Versuche zur Herstellung eines «Bis(triasterans)» und Synthese des heterocyclischen (Tricyclo[4.4.1.01,6]undeca-3,8-dien-11,11-dimethyl)sulfits

Tentative Synthesis of ‘Bis(triasterane)’ and Synthesis of the Heterocyclic (Tricyclo[4.4.1.0^1,6]undeca-3,8-diene-11,11-dimethyl)sulfite The synthesis of the bis(triasterane) ( 1 ) has been tried; the reaction of ‘isotetraline’ (1,4,5,8-Tetrahydronaphthalene; 2 ) with diazomalonate yielded the tricyclic systems 5 and 6 , and not 4 . Hydrolysis of 5 gave the monocarboxylic acid 7 , and not the dicarboxylic acid 9 . The latter could be obtained from the dibromoderivative 8 , but 9 couldn't be converted to the acyl chloride 10 . The reduction of 9 with LiAlH₄ yielded the crystalline diol 11 , which was cyclized with SOCl₂ to the heterocycle 12 . The spectral data of the new compounds 5, 6, 7, 11 and 12 are reported and discussed.     

Fluorocyclohexanes part XV [1] dehydrofluorinations of undeca- deca- and nona- fluorocyclohexanes

An experimental modification has improved dehydrofluorinations of undeca- deca- and nona- fluoroeyclohexanes, and enhanced the proportions of dienes and aromatics formed.