Tris(dimethylamino)methane

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[5762-56-1] C7H19N3 (MW 145.29) InChI = 1S/C7H19N3/c1-8(2)7(9(3)4)10(5)6/h7H,1-6H3 InChIKey = MUMVIYLVHVCYGI-UHFFFAOYSA-N (reactive aminomethylenating reagent (formylating reagent) for CH2- and NH2-acidic compounds; can serve as a source for bis(dimethylamino)carbene) Alternate Names: TDAM; N,N,N′,N′,N″,N″-hexamethylmethanetriamine. Physical Data: bp 42–43 °C/12 mmHg; n20D = 1.4360. Solubility: miscible with nonpolar aprotic, water-free solvents; reacts with protic solvents such as water, alcohols, and even aprotic, weak CH-acidic solvents such as acetone and acetonitrile on heating. Form Supplied in: colorless to light yellow liquid; strong amine smell. Analysis of Reagent Purity: 1H NMR spectrum of a neat sample. Preparative Methods: can be prepared by reaction of lithium dimethylamide with either N,N,N′,N′-tetramethylformamidinium salts2 or bis(dimethylamino)acetonitrile (eqs 1 and 2).3 The lithium dimethylamide solution can be prepared from lithium, dimethylamine, and naphthalene in dry THF.4 Lithium dimethylamide can be replaced by sodium dimethylamide,2 which is accessible in situ from Sodium Hydride, dimethylamine, and catalytic amounts (≈20%) of Trimethyl Borate.5 (1) (2) In the reaction of tetramethylformamidinium chloride with triphenylphosphonium ylides, TDAM is formed as a byproduct.6 TDAM is also obtained as a byproduct in the synthesis of alkanethiobis(dimethylamino)methanes from sodium alkanethiolates and N,N,N′,N′-tetramethylformamidinium methylsulfate or from aminal esters and alkanethiols by disproportionation of the primary products.7 Triethyl Orthoformate reacts with lithium dimethylamide (prepared in situ from lithium and dimethylamine) in HMPA to give TDAM.8 In an equilibrium reaction, DMF acetals react with dimethylamine to give TDAM.9 This reaction can be used on a preparative scale, if the dimethylamine is introduced at about 100 °C in the presence of 2,4,6-trimethylphenol as catalyst.10 The transamination of bis(dimethylamino)alkoxymethanes with excess dimethylamine affords TDAM.11 TDAM is produced in good yields in the reaction of tetrakis(dimethylamino)titanium with N,N-Dimethylformamide in ether (eq 3).12 (3) Good yields of TDAM can be obtained by reduction of N,N,N′,N′,N″,N″-hexamethylguanidinium chloride with a mixture of sodium hydride and Sodium Bis(2-methoxyethoxy)aluminum Hydride (75%)13 or by a mixture of sodium hydride and trimethyl borate (eq 4).5 (4) Handling, Storage, and Precautions: should be handled and used with strict exclusion of atmospheric moisture. The product should be stored in a tightly sealed container under a dry nitrogen or argon atmosphere in a refrigerator or freezer. Use in a fume hood.