1. The oxidation with nitrogen oxides of primary hydroxyl groups in the openglucopyranoside ring of the cellulose macromolecule was investigated. The typical reaction of the oxidation of the primary hydroxyl groups in the anhydroglucose unit is inhibited to a considerable extent in open glucopyranoside rings. 2. The selective oxidation with nitrogen oxides of the OH group at C6 in the cellulose molecule is due to the presence and nature of the glucopyranoside ring.