Iodine Nitrate

Abstract

[14696-81-2] INO3 (MW 188.91) InChI = 1S/INO3/c1-5-2(3)4 InChIKey = CCJHDZZUWZIVJF-UHFFFAOYSA-N (additions to alkenes;1-7 regioselective and stereoselective introduction of the iodine and oxygen (nitrate) function;1-6, 8 in the case of INO2, introduction of iodine and nitro groups;6c,7 iodination of alkylbenzenes9) Physical Data: prepared in situ in solution.1, 2 Solubility: sol most organic solvents. Form Supplied in: not available commercially; prepared in situ. Preparative Methods: iodine nitrate (INO3) and iodine nitrite (INO2, more appropriately called nitryl iodide) often show similar chemical properties and can be prepared in situ from iodine and silver nitrate or silver nitrite, respectively. The first reported4 preparation of INO3 was from Mercury(II) Nitrate and Iodine in ether. Silver(I) Nitrate and I2 in ether, acetonitrile, or MeOH, as well as AgNO3 and Iodine Monochloride in CHCl3–pyridine, have been used successfully for additions to alkenes,1, 4 although the latter reagent also leads to iodopyridinium adducts.1 Nitrogen Dioxide and I2 have also been used to generate INO3.2 The first reports7 of INO2 addition to alkenes employed Silver(I) Nitrite and I2 in ether to produce iodo nitro adducts, but this reagent also can lead to INO3 adducts.6c,7 A typical procedure for addition of INO3 to alkenes is as follows:1 to AgNO3 (6.8 g, 0.04 mol) in 50 mL dry CHCl3 and 15 mL anhyd. pyridine is added dropwise 6.5 g (0.04 mol) ICl in 20 mL CHCl3. AgCl is filtered and washed with CHCl3–pyridine and 0.04 mol of (E)-4,4-dimethyl-2-pentene is added. After 3 h of stirring, the mixture is poured into ether, filtered, and concentrated to yield 8.7 g (76%) of erythro-3-iodo-4,4-dimethyl-2-pentyl nitrate and 5% of an iodopyridinium salt. A typical procedure for INO2 addition is as follows:7 AgNO2 (7.55 mmol) and I2 (15.1 mmol) in 75 mL ether is stirred for 30 min and 2-cholestene (7.55 mmol) is added under N2. Workup after 4 h gives 2.033 g (51%) of 2β-iodo-3α-nitrocholestane and 5% (by IR) of 3α-iodo-2β-cholestanyl nitrate. Handling, Storage, and Precautions: solutions of INO3 or INO2 are not stable on standing. These reagents should be handled in a fume hood.