Dibenzo nitration

HjO), a picrate, m.p. 253° (dec.) and furnishes a dibenzoate, whose sulphate has [a] ° + 52-1° (EtOH) and hydrochloride, B. HCl. 2H2O, m.p. 115° or 205° (dry), + 41-8° (dilute alcohol) and nitrate, B. HNO3, m.p. 197°. On reduction with hydriodic acid and red phosphorus the dihydroxytropane is converted into tropane and on treatment with phosphorus oxychloride it yields a base, CgHjgON, b.p. 188°/752 mm., picrate, m.p. 177° (dec.). This dihydroxytropane is probably represented by formula (XIII).The dibenzoyl-derivative has local ansesthetic properties. The wovaleryl ester is the alkaloid valeroidine found in Duboisia myoporoides (p. 90). 

The central C-C double bond of dibenz[, /]oxepin displays the properties of an activated aromatic system and undergoes substitution reactions. Nitration and acid-catalyzed dcutcration gives the dibenzo[i>,/]oxepins 1 with the respective substituent in position 10.161... 

Complexes of alcohols like methanol, ethanol, 2-propanol and n-butanol (116-122), and ethers like Diox (47,120,123-125) and THF (126-128) have been prepared. The bonding between these ligands and the metal ions is considered to be very weak. In recent years, complexes of the lanthanides with a few macrocyclic polyethers have been reported. Cassol et al. (129) have prepared the complexes of benzo-15-crown-5 and dibenzo-18-crown-6 with lanthanide nitrates and isothiocyanates. King and Heckley (130) have also reported the complexes of these ligands with lanthanide nitrates. The heavier lanthanide nitrate complexes of dibenzo-18-crown-6... 

Katritsky and co-workers ° reacted primary amines with the triflate salt of 5,6,8,9-tetrahydro-7-phenyl-dibenzo[c, /tjacridine to generate the corresponding A -substituted acri-dinium triflate salts, which on refluxing in dioxane in the presence of benzyltrimethylammo-nium nitrate, yield the corresponding nitrate esters. 

NOTE Higher nitrated derivs of Dibenzo-furan were not found in Beil or in CA thru 1961... 

The situation with different metals is almost opposite. It was shown that the influence of dibenzo-24-crown-8, dicyclohexyl-18-crown-6 (DCH18C6), or trioctylphos-phine oxide on the extraction of europium by dinonylnaphthalenesulfonic acid (HDNNS) in benzene from nitrate and perchlorate solutions is negative. That is, an antisynergistic or antagonistic effect is observed.53... 

Boule P, Hutzinger O. 1987. Photoreactivity of dibenzo-para-dioxins - can chlorodibenzo-para-dioxins be nitrated in the environment. Toxicol Environ Chem 13 229-256. 

Unusually, chloride is foimd in the first coordination sphere of lanthanum as well as nitrate in the serendipitously discovered mixed anion complexes [EaCl2(N03)(12-crown-4)]2 and [LaCl2(N03)(18-crown-6)]. A few complexes have been reported with other halides, such as [Sml3(dibenzo-18-crown-6)] (tricapped trigonal prismatic) and [LaBr3(12-crown-4)(acetone)] (distorted square antiprismatic). Lanthanide thiocyanate complexes of crown ethers are now starting to be studied. Several thiocyanate complexes of the... 

Radical 80 has been prepared as its perchlorate salt by anodic oxidation in ethyl acetate in the presence of hthium perchlorate. The reactivity toward nucleophiles of material so prepared was investigated nitrite and nitrate ions give 2-nitrodibenzo[l,4]dioxin although the mechanisms of the reactions are not clear. Pyridine gives 7V-(2-dibenzo[l,4]dioxinyl)pyridinium ion (84). Other nucleophiles acted as electron donors and largely reduced 80 back to the parent heterocycle they included amines, cyanide ion and water. In an earlier study, the reaction of 80 with water had been examined and the ultimate formation of catechol via dibenzo[l,4]dioxin-2,3-dione was inferred. The cation-radical (80) has been found to accelerate the anisylation of thianthrene cation-radical (Section lII,C,4,b) it has been found to participate in an electrochemiluminescence system with benzo-phenone involving phosphorescence of the latter in a fluid system, and it has been used in a study of relative diffusion coefficients of aromatic cations which shows that it is justified to equate voltammetric potentials for these species with formal thermodynamic redox potentials. The dibenzo[l,4]dioxin semiquinone 85 has been found to result from the alkaline autoxidation of catechol the same species may well be in-... 

One way of improving SFE efficiency is by using a more suitable SF to extract the target analyte. Unfortunately, the choice of fluids other than CO, is restricted by the desire to have reasonable critical parameter values and costs, chemical inertness, low toxicity and little environmental impact. The use of supercritical N2O has proved to increase the extraction efficiency for high-molecular weight PAHs and chlorinated dibenzo-p-dioxins from fly ash and sediment [52]. This extractant, however, does not always improve the extraction efficiency [53] also, it can be explosive in the presence of reactive organics. Other polar fluids such as CHCIF, (Freon-22) have exhibited increased efficiency in the extraction of nitrated and non-nitrated PAHs from particulate matter in diesel exhaust [54]. Freon-22 has also been found to allow significantly fast and effective extraction of... 

There are several examples of crown ether complexes where yttrium is not bound to the crown ether. [Y(H20)8]C13 (15-crown-5) has a [Y(H20)8]3+ cation (distorted dodecahedron) with the crown ether and chloride hydrogen bonded to the coordinated water molecules.58,225 An aqueous solution containing yttrium triflate and 18-crown-6 produces crystals of [Y(CF3-COO)2(H20)6](CF3COO),(18-crown-6) which have the crown ether hydrogen bonded to the coordinated water molecules.226 The complex [Y(N03)3(H20)3] (dibenzo-24-crown-8) has a nine-coordinate yttrium formed by bonding to three bidentate nitrate groups and three water molecules. The crown ether is hydrogen bonded to the water molecules.227... 

Fig. 4.8. Extraction of a) alkali metal nitrates and b) cesium picrate and nitrate with dibenzo-18-crown-6 (2) in CHCI3.

It must be stressed that factors such as the hydration (or solvation) of the metal ion and anion effects on the extracted complex often make it difficult to predict the order of extractability for such systems. Such factors may even influence the stoichiometry of the extracted species. Thus, the simple match of the metal to the whole concept is only of limited utility. For example, potassium, rubidium and sodium nitrates are extracted in the presence of dibenzo-18-crown-6 (2) as 1 1 1 complexes. On the other hand, cesium forms a 1 2 1 sandwich complex with this crown (metal crown nitrate) in the organic phase and this affects the extraction order for the above metal ions, with the order being dependent on ligand concentration. In contrast, for picrate as the anion the composition of the extracted cesium complex is 1 1 1 (Fig. 4.8) [27]. 

---