The X-ray diffraction crystal structure determination and electron impact fragmentations of the gaseous ions of 3-(p-chlorophenyl)-1-methyltriazene-1-oxide and its 3-methyl derivative

The decomposition of the gaseous positive ions of the title compounds obtained by electron impact have been completely mapped. The X-ray structural determinations of these two substances established their identity definitively and allowed to reveal some interesting features of these molecules of pharmaceutical interest.     

Rigidified calixarenes bearing four carbamoylmethylphosphineoxide or carbamoylmethylphosphoryl functions at the wide rim

Conformationally rigidified tetraCMPO derivatives have been prepared from calix[4]arene bis(crown ether) 4a in which adjacent oxygens are bridged at the narrow rim by two diethylene glycol links. Acylation of the tetraamine 4c with the CMPO-active ester 5b gave the tetraphosphine oxide 6a, while the tetraphosphinate 6b and the tetraphosphonate 6c were obtained by Arbuzov reaction of tetrabromoacetamido derivative 7 with PhP(OEt)2 or P(OEt)3. The extraction ability of these CMPO derivatives was checked for selected lanthanides and actinides and compared with the analogous compounds 1b, 10b and 10d derived from calix[4]arene tetrapentyl ether. All rigidified bis(crown ether) ligands are more effective extractants than their pentyl ether counterparts and require only 1/10 of the concentration (cL= 10 4M) to obtain the same distribution coefficients, while with CMPO itself a 2,000-fold concentration is necessary. This could be a consequence of a better preorganisation of the ligating functions owing to the rigidity which on the other hand did not change the observed selectivity for americium (DAm/DEu=9-19) and for light lanthanides over heavy ones. NMR relaxivity titration curves show that the complex of Gd3+ with ligand 6a is highly oligomerised in anhydrous acetonitrile over a large range of ligand:metal concentration ratios. Nuclear magnetic relaxation dispersion (NMRD) profiles also showed that large oligomers were formed, and their mean tumbling times were deduced from the Solomon-Bloembergen-Morgan equations. The NMR spectra of dia- and paramagnetic lanthanide complexes with 6a agreed with the presence of two conformers with an elongated calix[4]arene skeleton in which the distances between opposite methylene groups are different. Contrary to what was observed with ligand 2a, the addition of nitrate ions does not labilize the metal complexes, presumably because of the rigidification effect of the ether bridges. Single-crystal X-ray structures were obtained for the active ester 5b and for diphenylphosphorylacetic acid 5a.     

X-ray crystal structure of the copper(II)bis(2,2′-dipyridyl)dithiocarbamate,produced by an unusual reaction of CS2 with Cu−N bonds

The title compound was obtained from a CS₂ solution of bis(2,2-dipyridylamido)copper(II), by insertion of solvent into this complex. In the structure of the dithiocarbamate the metal atom is approximately square-planar coordinated by four S atoms from two chelating ligands. Considering the long interactions between the metal center and the S(2) atom from a centrosymmetrically related complex [Cu(1)...S(2)=3.230 Å], double bridged dimers are formed with the copper atoms in an elongated square-pyramidal coordination. The crystals are monoclinic, space groupP2 ₁/n witha=14.549(3),b=11.662(3)c=15.329(4) Å and =114.79(2)°.     

Reactions of aromatic nitro compounds with acetophenone in the presence of alkali. Crystal structure of (E)-1,2-dibenzoyl-o-tolylaminoethylene

Methyl and methoxy substituted nitroarenes were reacted with acethophenone in the presence of sodium ethoxide in ethanol giving arylamino-conjugated diketo derivatives. A case ofipso-substitution of a methoxy group is discussed. The title compound C₂₃H₁₉NO₂ (M _r =341.4) crystallizes in the monoclinic system, space groupP2₁/n witha=21.579(4),b=8.526(2),c=9.983(2) Å;=92.3(1)°;V=1835.2(7) ų,Z=4,D _c =1.24 g cm^–3,(Cu-K )=5.9 cm^–1, =1.5418 Å,F(000)=720. The molecule adopts theE configuration with the C=O carbonyl groupstrans with respect to the ethylenic double bond.