Tris(dimethylamino)methane
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| Names | |
|---|---|
| Preferred IUPAC name
N,N,N′,N′,N′′,N′′-Hexamethylmethanetriamine | |
| Other names
N,N,N,N,N,N-hexamethylmethanetriamine [bis(dimethylamino)methyl]dimethylamine | |
| Identifiers | |
3D model (JSmol) |
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| ChEMBL | |
| ChemSpider | |
| ECHA InfoCard | 100.024.804 |
| EC Number |
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PubChem CID |
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| UNII | |
CompTox Dashboard (EPA) |
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| Properties | |
| C7H19N3 | |
| Molar mass | 145.250 g·mol−1 |
| Hazards | |
| GHS labelling: | |
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| Danger | |
| H225, H314 | |
| P210, P233, P240, P241, P242, P243, P260, P264, P280, P301+P330+P331, P302+P361+P354, P303+P361+P353, P304+P340, P305+P354+P338, P316, P321, P363, P370+P378, P403+P235, P405, P501 | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Tris(dimethylamino)methane (TDAM) is the simplest representative of the tris(dialkylamino)methanes of the general formula (R2N)3CH in which three of the four of methane's hydrogen atoms are replaced by dimethylamino groups (−N(CH3)2).[1] Tris(dimethylamino)methane can be regarded as both an amine and an orthoamide.
Tris(dimethylamino)methane is a strong base and can be used as a formylation agent, as aminomethylenation reagent and as a source for the basic bis(dimethylamino)carbene of the formula (R2N)2C:.[2]
Tris(dimethylamino)methane is formed in the reaction of N,N,N′,N′-Tetramethylformamidinium chloride (TMF-Cl)[1][3][4] or bis(dimethylamino)acetonitrile[5] with lithium dimethylamide or sodium dimethylamide with yields between 55 and 84%.[2]
Synthesis of TDAM from TMF-Cl and lithium dimethylamide
From dimethylamine and trimethoxyborane sodium dimethylamide is formed in situ in the presence of sodium hydride which reacts with N,N,N′,N′-tetramethylformamidinium chloride in 84% yield to tris(dimethylamino)methane and with bis(dimethylamino)acetonitrile in 77% yield.[6]
Synthesis of TDAM from TMF-Cl and sodium dimethylamide with trimethoxyborane
The reaction of the dimethylformamide (DMF) dimethylacetal, HC(OCH3)2N(CH3)2, (from the DMF–dimethyl sulfate complex and sodium methoxide[7]) with dimethylamine in the presence of the acidic catalyst 2,4,6-tri-tert-butylphenol (which is largely stable to the alkylating agent) produces tris(dimethylamino)methane.[8]
Synthesis of TDAM from the dimethylacetal of DMF
Tris(dimethylamino)methane is formed in good yield (83%) in the reaction of DMF with tetrakis(dimethylamino)titanium(IV).[9]
Synthesis of TDAM from DMF with tetrakis(dimethylamino)titanium(IV)
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N,N,N′,N′,N″,N″-Hexamethylguanidinium chloride (readily obtainable by dimethylamine and N,N,N′,N′-tetramethylchloroformamidinium chloride derived from tetramethylurea and phosgene[10]) forms tris(dimethylamino)methane in 53% yield under the exposure of the reducing agent sodium bis(2-methoxyethoxy)aluminium hydride (Red-Al).[11]
Sodium hydride and trimethyl borate reduce N,N,N′,N′,N″,N″-hexamethylguanidinium chloride in 80% yield to tris(dimethylamino)methane.[6]
Synthesis of TDAM from hexamethylguanidinium chloride
Properties
Tris(dimethylamino)methane is a clear, colorless or pale yellow liquid with a strong ammoniacal odor. The compound is freely miscible with many non-polar aprotic and water-free solvents. However, when heated tris(dimethylamino)methane reacts with protic solvents (such as water or alcohols) but also with weak CH-acidic substances, such as acetone or acetonitrile.[2]
Upon heating to 150–190 °C decomposition occurs with the formation of tetrakis(dimethylamino)ethene,[12] a strong electron donor.[13]
Synthesis of tetrakis(dimethylamino)ethene
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