The monotosylates obtained by treatment of α- and β- cyclodextrin with p- methylbenzenesulfonyl chloride reacted with ammonia to give the title compounds. These amines are of unusually low basicity , with pKa values of 8.70 and 8.72, respectively. In water at 25°, the hydrochloride salt of the amine derived from β- cyclodextrin is approximately 40 times more soluble than β-cyclodextrin and, through complexation, the salt increases the solubility of Nabumetone over 800 times.

Phosphorus-32 tracer experiments have demonstrated that the phosphato ligand in [Co en2PO4]0 [Co(NH3)4PO4]O, [CO(NH3)4OH2HPO4]+, and [Co en2OH2.HPO4]+ undergoes slow substitution in acid and alkaline media at 40-60� and that a reversible hydrolysis equilibrium is established from pH 3 to 11. Outside this pH range, acid and base hydrolysis of all these phosphato complexes to diaquo or dihydroxo complexes is complete. The infrared spectra of [Co en2PO4]0 and [Co(NH3)4PO4]0 are consistent with a bidentate phosphato structure and with a monodentate phosphato ligand in CO(NH3)5PO4 and probably [Co(NH3)4OH2HPO4]+I-. The bidentate and monodentate complexes may be rapidly and reversibly interconverted but significant concentrations of the bidentate complexes only persist in the range pH 5.5-7.5. P.m.r, studies have established the predominantly cis configuration of the aquophosphato complexes. These complexes exhibit four acidity constants, one due to the aquo ligand, and three due to the monodentate phosphato ligand. The bidentate [Co en2PO4]0 exhibits a single acidity constant above pH 2. The aquophosphato complexes undergo both acid and base hydrolysis entirely by Co-O bond rupture. Acid hydrolysis of [Co en2PO4]0 also proceeds entirely by Co-O bond rupture but at pH 6.8 and in 0.25M NaOH hydrolysis proceeds by 60-65% Co-O bond rupture and by 30-35% P-O bond rupture.

The preparation of the new ligand 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane, (-N(Me)-(CH2)2-)4 (= L), and the complexes [NiL] (ClO4)2, [NiL(OCHNMe2)] (ClO4)2, [NiLN3] ClO4, [CuL] (ClO4)2, and [NiY] (ClO4)2, where Y = (-N(Me)(CH2)2N(Me)(CH2)3-)2, 1,4,8,11-tetra-methyl-1,4,8,11-tetraazacyclotetradecane, are described. The magnetic moments of the nickel((11) species are reported, and the labile low-spin/high spin equilibria characterizing the [NiLI2+ and [NiY]2+ systems over a range of temperatures and ionic strengths in aqueous solution are discussed. The spectrophotometric titration of the aqua ligands in [NiLH2O]2+, [CuLH2O]2+, and [NiYH2O]2+ against sodium hydroxide yields pKa values of 10.2 � 0.2, 12.0 � 0.3 and 10.7 � 0.2, respectively, and a study, using Job's method of continuous variations, of the formation of azide species shows [NiLN3]+ and [NiYN3]+ to be formed predominantly in aqueous solution.

Reactions of amino-substituted cyclodextrins with bis(3-nitrophenyl) oxalate, malonate, succinate and glutarate, and with diphenyl carbonate, afford a range of linked cyclodextrins. These include α- and β-cyclodextrin dimers, joined by substitution at either C6 or C3, and asymmetric species with a β-cyclodextrin bonded to an a-cyclodextrin and a C3-substituted cyclodextrin attached to a C6-substituted moiety.

The carbon-13 N.M.R. chemical shifts for a series of para-substituted N,N-dimethylbenzamides have been measured. The substituent induced 13C shifts have been examined by a dual substituent parameter (DSP) method using Hammett-type constants. The barriers to rotation have also been correlated with Hammett-type constants by the DSP method and related to 13C substituent induced shifts. Substituent effects of the bromomethyl, dibromomethyl and tribromomethyl groups have been examined by using the chemical shift and rotational barrier probes.