Inclusion Compounds of Cyclotriveratrylene (2,3,7,8,12,13-hexamethoxy-5,10-dihydro-15H-tribenzo[a,d,g]cyclononene) with Chlorinated Guests

Inclusion compounds were formed between the host cyclotriveratrylene, H, (2,3,7,8,12,13-hexamethoxy-5,10-dihydro-15H-tribenzo[a,d,g]cyclononene) and the guests carbon tetrachloride, 1,1,1-trichloroethane, 1,1,1-trichloropropane and 1,1,2-trichloroethane. 1 (H·CCl₄) has guest molecules in channels alternating with channels of host molecules. 2 (H·C₂H₃Cl₃·C₃H₅Cl₃) and 3 (H·2C₂H₃Cl₃) exhibit a slightly different packing arrangement with one guest molecule in the host cavity and the rest of the guest molecules in channels. The stability and reactivity of these inclusion compounds were investigated.     

Synthese du noyau dihydro-5,6 s-triazolo[2,3-d] henzoxazepine-1,4

2-Ethylthio-5 methylene-6H-s-triazolo[2,3-d][1,4] benzoxaze-pine, a new heterocyclic ring system, has been synthesized by cyclisation of the appropriate propargyloxyphenyltriazole. Nucleophilic addition of a triazole nitrogen atom also yields three isomeric by-products, mainly a s-triazolo[2,3-e] [1,5]benzoxazocine.     

Eight-membered heterocycles. 12H-dibenzo[d,g][1,3,2]dioxaphosphocin and 12H-dibenzo[d,g][1,3,2]dioxaborocin derivatives

The synthesis of phosphonite and thiophosphite derivatives of the 12H-dibenzo[d,g][1,3,2]dioxaphosphocin ring system is described. The 'H nmr shows evidence for long-range coupling of the C-12 methine proton to phosphorus. The ¹H nmr of the 12H-dibenzo[d,g][1,3,2]dioxaborocin ring system is compared to that of the phosphorus analog. The nmr spectral data suggest that the phosphorus and boron containing ring systems have similar ring conformations.     

5-[2-(对苯偶氮苯氧基)丁氧基]苯基-10,15,20-三[(对甲氧基苯基)]卟啉及其金属配合物的合成

以5-[2-(4-溴丁氧基)苯基]-10,15,20-三(对甲氧基苯基)卟啉和对羟基偶氮苯为原料,经取代反应合成新化合物5-[2-(对苯偶氮苯氧基)丁氧基]苯基-10,15,20-三[(对甲氧基苯基)]卟啉(2),2经配位反应合成了金属铜,锌配合物(2a)和(2b),其结构经UV-Vis,1H NMR,IR和元素分析表征。     

Eight-membered organosulfur heterocycles. Synthesis of dibenzo[d,g][1,3,6,2]dioxathiaphosphocin and dibenzo[d,g][1,3,6,2]dioxathiasilocin ring systems

The reaction of 2,2′-thiobisphenols with either phenylphosphonous dichloride or phosphorus trichloride followed by an alcohol gave derivatives of the dibenzo[d,g][1,3,6,2]dioxathiaphosphocin ring system. The analogous reaction of 2,2′-thiobisphenols with alkyl and aryl dichlorosilanes gave the heretofore unreported dibenzo[d,g][1,3,6,2]dioxathiasilocin ring system. The analytical and spectral data are reported.     

Electronic Structure and Photophysical Properties of Isoindole and its Benzo[f]- and Dibenzo[e,g]-Derivatives

The synthesis of N-methyl-benz[f]isoindole ( 2 ) and N-methyl-dibenz[e,g]isoindole ( 3 ) is reported. The NMR. spectra of N-methyl-isoindole ( 1 ) and of 2 have been analysed and the implications concerning the alternation of bond lengths are discussed. The photophysical properties of 1 to 3 have been investigated by the following methods: HeI photoelectron (PE.) spectroscopy, UV./VIS. absorption (polarization measurements by the stretched-foil technique) and emission spectroscopy (fluorescence spectra, lifetimes and quantum yields, phosphorescence spectra), and flash spectroscopy (triplet-triplet absorption spectra). The discussion of the results is based on HMO. and PPP SCF CI. calculations and points to the relationship between the heterocycles 1 to 3 and the corresponding benzenoid hydrocarbons obtained by replacement of the ? NMe? subunit by ? CH?CH? . Some comments concerning the ground state properties of isoindole and related compounds are derived from the analysis of their electronic structure.     

Synthese und NMR-spektroskopische Untersuchungen von Dibenzo[d,g]-1,3-dioxa-2-element-6-silocinen

Synthesis and NMR Spectroscopic Investigations of Dibenzo [d,g]-1,3-dioxa-2-element-6-silocine Bis-(o-halogenoaroxy)silanes react with sodium via metallation and a fast two-step [1.3]-rearrangement to the sodium salts of bis(o-hydroxyaryl)silanes. These are cyclized in a one-pot-reaction with element halides of silicon, phosphorus and arsenic to the title compounds of the general formula R¹R²Si(C₆H₄O)₂E (E = SiR₂, P(Y)R, As(Y)R). One conformer is prefered according to N.M.R. spectroscopical investigations.     

Reactivite des carbanions benzyliques : VI. Structure et reactivite du trimethylsilyl-9 dihydro-9,10 anthracene; preparation des bis(trimethylsilyl)-9,9 et trimethylsilyl-9 alkyl-9 dihydro-9,10 anthracenes

The structure of 9-trimethylsilyl-9,10-dihydroanthracene (Me₃SiDHA) has been studied by NMR; the coupling constants of the three 9,10 protons do not change at between 25 and 90°C (ABM spectrum; J_AB }- 18.2; J_AM ? 1.2; J_BM ? 0.3 Hz in toluene-d₈), indicating that the Me₃Si group prefers the quasi axial position. In the presence of BuLi in THF, Me₃SiDHA reacts with Me₃SiCl to yield three new products: 9,9-bis(trimethylsilyl)-9,10-dihydroanthracene (IId) (major), (9,10-dihydroanthracen-9-yl)dimethylsilyl(trimethylsilyl)methane (V) and (9-trimethylsilyl-9,10-dihydroanthracen-9-yl)dimethylsilyl(trimethylsilyl)-methane (VI) together with the known 9,10-bis(trimethylsilyl)-9,10-dihydroanthracene (cis and trans). The carbanion of Me₃SiDHA can also be alkylated (alkyl  Me, Et, i-Pr) to the new 9,9-disubstituted derivatives: 9-Me₃Si-9-alkyl-DHA.The formation of the carbanion of Me₃SiDHA has been investigated and reveals a competition in the abstraction by the base of H₉ and H₁₀; the latter is less crowded but the 9-carbanion is stabilized by the vicinity of the silicon atom. The carbanion obtained from Me₃SiDHA reacts exclusively at C(9) with D₂O. A study of the alkylation of 9-trimethylsilyl-9-deuterio-9,10-dihydroanthracene shows that the generation of the 10-carbanion is followed by a 1,4 hydrogen rearrangement which yields the 9-carbanion. The mechanism is discussed and the roles of Me₃Si and t-Bu are compared in the DHA series.