Dimethyl(methylene)ammonium Iodide

(1; X = I−) [36627-00-6] C3H8IN (MW 185.02) InChI = 1S/C3H8N.HI/c1-4(2)3;/h1H2,2-3H3;1H/q+1;/p-1 InChIKey = VVDUZZGYBOWDSQ-UHFFFAOYSA-M (2; X = Cl−) [30438-74-5] C3H8ClN (MW 93.57) InChI = 1S/C3H8N.ClH/c1-4(2)3;/h1H2,2-3H3;1H/q+1;/p-1 InChIKey = ZJTROANVDZIEGB-UHFFFAOYSA-M (3; X = CF3CO2−) [85413-84-9] C5H8F3NO2 (MW 171.14) InChI = 1S/C3H8N.C2HF3O2/c1-4(2)3;3-2(4,5)1(6)7/h1H2,2-3H3;(H,6,7)/q+1;/p-1 InChIKey = YPMYDJDJOCCNSE-UHFFFAOYSA-M (electrophilic aminomethylation (Mannich reaction) agent which condenses with active methylene compounds,1 organometallic reagents,2 and electron-rich aromatics and heteroaromatics3 to produce tertiary amines; useful for the synthesis of α,β-unsaturated carbonyl compounds by elimination of the dimethylamino group1) Alternate Names: (1) Eschenmoser's salt; (2) Bohme's salt. Physical Data: (1) mp 219 °C (dec). (2) mp 116 °C. (3) bp 100 °C/14 mmHg. Solubility: sol DMF; partially sol4 MeCN, CH2Cl2, THF (reactions in these solvents occur even though the reagent is not completely soluble). Form Supplied in: salts (1) and (2) are widely available as solids. Preparative Methods: salt (1) is prepared by thermolysis of (iodomethyl)trimethylammonium iodide5 or cleavage of N,N,N′,N′-tetramethylmethanediamine by TMSI.6 It is purified by recrystallization from tetrahydrothiophene dioxide or by sublimation at 120 °C/0.05 mmHg.5 Salt (2) is prepared by cleavage of N,N,N′,N′-tetramethylmethanediamine by AcCl7 or cleavage of methyl dimethylaminomethyl ether by TMSCl.8 Salt (3), a liquid, is prepared by Polonovksi reaction of trimethylamine oxide with TFAA or cleavage of N,N,N′,N′-tetramethylmethanediamine with TFA. It is purified by distillation.9 Handling, Storage, and Precautions: salts (1)–(3) are very hygroscopic and must be used under anhydrous conditions to preserve their reactivity.

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