The isobutane chemical ionization (CI) mass spectra of cis- and trans-1-butyl-3- and -4-dimethylaminocyclohexanols and of their methyl ethers exhibit abundant [MH - H(2)O](+) and [MH - MeOH](+) ions respectively. On the other hand, only the MH(+) ions of the cis-isomers exhibit significant [MH - H(2)O](+) and [MH - MeOH](+) ions under collision-induced dissociation (CID) conditions. The non-occurrence of water and methanol elimination in the CID spectra of the trans-isomers indicates retention of the external proton at the dimethylamino group in the MH(+) ions that survive after leaving the ion source and the first quadrupole of the triple-stage quadrupole ion separating system, and the trans-orientation of the two basic sites does not allow proton transfer from the dimethylamino group to the hydroxyl or methoxyl. Such transfer is allowed in the cis-amino alcohols and amino ethers via internal hydrogen-bonded (proton-bridged) structures, resulting in the elimination of water and methanol from the surviving MH(+) ions of these particular stereoisomers upon CID. The abundant [MH - ROH](+) ions in the isobutane-CI mass spectra of the trans-isomers indicates protonation at both basic sites, affording two isomeric MH(+) ions in each case, one protonated at the dimethylamino group and the other at the less basic oxygen function. These results show that the isobutane-CI protonation of the amino ethers and amino alcohols is a kinetically controlled process, occurring competitively at both basic sites of the molecules, despite the large difference between their proton affinities ( approximately 25 and approximately 35 kcal mol(-1); 1 kcal = 4.184 kJ). Copyright 1999 John Wiley & Sons, Ltd.