Chlorine Azide, CIN₃. I¹

Abstract

tion of potassium hydroxide. The sample bottle was immersed in a water-bath from two to seven days and samples removed as convenient for analysis. The alkalinity was determined by titration with sulfuric acid solution using methyl orange indicator. The iodide content was determined gravimetrically as silver iodide. The density was determined by weighing a 25-ml. sample of the saturated solution. Weights were cor rected for the buoyant effect of air. All chemicals used were of Reagent grade.Equilibrium seemed to be quickly attained from the supersaturated condition. In certain experiments, equilibrium was approached from the uti dersaturated side and no significant variation in solubility was found.From a number of titrations for alkalinity in the equilibrium mixtures, it was determined that about 1% of the total alkalinity was in the form of carbonate. To estimate the magnitude of the effect of this impurity on the solubility determinations, one solution was prepared with added carbonate to give a carbonate alkalinity of 0.40 N in a total alkalinity of 6.453 N., i.e., 6.2%. The solubility point determined for this solution lies on the smooth curve drawn through the other experimental points, indicating that small proportions of carbonate are without appreciable effect on the solubility determinations. SummaryThe solubility of potassium iodide at 20°w as determined in potassium hydroxide solutions from 0 to 14.35 N in alkali. The density and solubility curves show no discontinuities.The accuracy of the results is estimated to be 0.5%.

Reactions of positive ions with ClN3 at 300K

“…The semi-logarithmic decays of Cl 2 and ClN 3 were observed to be linear in all cases. 1 Decay of the primary ion was ∼20% for the slowest reactions and up to 80% for faster reactions. Due to the difficulties of this experiment we assign large error bars of ±35% to the reaction rate constants and ±40% of the minor products to the product ion branching ratios, if numbers are assigned.…”

“…While their explosive nature has been a deterrent to an in-depth study of their reactivity [1], interest in their applications has renewed importance. Theoretical studies have predicted a cyclic N 3 isomer resulting from photodissociation [2][3][4].…”

New Strategies for the Synthesis of Aliphatic Azides

“…Although numerous synthetic procedures have been developed for the 1,2-chloroazidation of alkenes for the synthesis of 1,2-chloroazides, none of them are generally adopted by synthetic chemists due to the lack of selectivity, low yields, toxic or exotic reagents, and excess base usage. − In 2015, Finn developed a safe and reliable method for the generation of ClN 3 from the treatment of sodium azide with hypochlorite and acetic acid under bibasic conditions, which was rapidly trapped by alkenes 167 to generate vicinal chloroazides 168 in moderate to good yields (Scheme a) . In the subsequent year, Hamashima and colleagues reported the chloroazidation of alkenes 167 using 1-chloro-1,2-benziodoxol-3-(1 H )-one as the chlorine source and TMSN 3 as the nucleophilic azide precursor at room temperature (Scheme b).…”

Taming Chlorine Azide: Access to 1,2-Azidochlorides from Alkenes

“…A solution of chlorine azide in organic solvents can be stored for several days at room temperature, , although we do not recommend this. From its discovery in 1908 through 1965, only several examples of the formation of ClN 3 [from HClO–HN 3 , Cl 2 –AgN 3 , , and Cl 2 –NaN 3 ] were described; none were generally adopted by synthetic chemists. But some interesting reports then began to appear, such as the method by Minisci and co-workers [FeCl 3 –H 2 O 2 –NaN 3 ] in which either two azido groups (related to Pb­(OAc) 4 –TMSN 3 ) , or an azido group and a chlorine atom were added to an unsaturated substrate via a radical mechanism.…”