Tetrakis(dimethylamino)ethylene

Tetrakis(dimethylamino)ethylene
Names
	Preferred IUPAC name N1,N1,N′1,N′1,N2,N2,N′2,N′2-Octamethylethene-1,1,2,2-tetramine
	Other names Octamethyl-ethenetetramine; TDAE
Identifiers
CAS Number	996-70-3;
3D model (JSmol)	Interactive image;
ChemSpider	63634;
ECHA InfoCard	100.012.398
EC Number	213-638-1;
PubChem CID	70455;
UNII	P6737B68MN;
CompTox Dashboard (EPA)	DTXSID0061371 ;
	InChI InChI=1S/C10H24N4/c1-11(2)9(12(3)4)10(13(5)6)14(7)8/h1-8H3 Key: CBXRMKZFYQISIV-UHFFFAOYSA-N;
	SMILES CN(C)C(=C(N(C)C)N(C)C)N(C)C;
Properties
Chemical formula	C10H24N4
Molar mass	200.330 g·mol−1
Appearance	colorless liquid
Density	0.861 g/cm3 (25 °C)
Melting point	−4 °C (25 °F; 269 K)
Boiling point	59 °C (0.9 mm Hg)
Hazards
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H226, H314
Precautionary statements	P210, P233, P240, P241, P242, P243, P260, P264, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P363, P370+P378, P403+P235, P405, P501
Flash point	53 °C (127 °F; 326 K)
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Tetrakis(dimethylamino)ethylene (TDAE) is an organic compound with the formula ((CH₃)₂N)₂C=C(N(CH₃)₂)₂, It is a colorless liquid. It is classified as an enamine. Primary and secondary enamines tend to isomerize, but tertiary enamines are kinetically stable.^[1] One unusual feature of TDAE is that it is a tetra-enamine. The pi-donating tendency of the amine groups strongly enhances the basicity of the molecule, which does exhibit properties of a typical alkene.^[2]

Reactions

TDAE reacts with oxygen in a chemiluminescent reaction to give tetramethylurea.^[3]^[4] The initial intermediate is (2+2) adduct, a 1,2-dioxetane. This species decomposes to electronically excited tetramethylurea. This returns to the ground state is accompanied by emission of green light with a maximum at 515 nm.^[5]

TDAE is an electron donor with E = 1.06 V vs Fc^+/0.^[6]

TDAE has been examined as a reductant in coupling reactions.^[7]

As one of many of examples of its redox behavior forms a charge-transfer salt with buckminsterfullerene:^[8]

C₂(N(CH₃)₂)₄ + C₆₀ → [C₂(N(CH₃)₂)₄⁺][C₆₀⁻] Oxidation affords a dication.

Structure

Crystallographic analysis show that TDAE is a highly distorted alkene, the dihedral angle for the two N2C termini is 28°. The C=C distance is alkene-like, 135 pm. The nearly isostructural tetraisopropylethylene also has a C=C distance of 135 pm, but its C6 core is planar. In contrast, [TDAE]²⁺ is an alkane with multi-C-N bonds.^[9]

Synthesis

It is available by pyrolysis of tris(dimethylamino)methane by pyrolysis^[10] or from chlorotrifluoroethene and dimethylamine.^[11]

References

^ Spitz, Cédric; Terme, Thierry; Vanelle, Patrice (2023). "1,1,2,2-Tetrakis(dimethylamino)ethene". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X. hdl:10261/236866. ISBN 978-0-471-93623-7.
^ David M. Lemal (1968). "Tetraaminoethylenes". In Saul Patai (ed.). The Amino Group. Patai's Chemistry of Functional Groups. pp. 701–748. doi:10.1002/9780470771082. ISBN 9780470771082.
^ H.E. Winberg; J.R. Downing; D.D. Coffman (1965), "The Chemiluminescence of Tetrakis(dimethylamino)ethylene", J. Am. Chem. Soc., vol. 87, no. 9, pp. 2054–2055, doi:10.1021/ja01087a039
^ "Chemilumineszenz von TDAE" (in German). illumina-chemie.de. 2014-08-08. Retrieved 2016-08-22.
^ H.E. Winberg; J. R. Downing; D. D. Coffman (1965). "The Chemiluminescence of Tetrakis(dimethylamino)ethylene". J. Am. Chem. Soc. 87 (9): 2054–2055. doi:10.1021/ja01087a039.
^ Broggi, Julie; Terme, Thierry; Vanelle, Patrice (2014-01-07). "Organic Electron Donors as Powerful Single-Electron Reducing Agents in Organic Synthesis" (PDF). Angewandte Chemie International Edition. 53 (2): 384–413. doi:10.1002/anie.201209060. PMID 24273111.
^ Kuroboshi, Manabu; Waki, Yoko; Tanaka, Hideo (2003). "Palladium-Catalyzed Tetrakis(dimethylamino)ethylene-Promoted Reductive Coupling of Aryl Halides". The Journal of Organic Chemistry. 68 (10): 3938–3942. doi:10.1021/jo0207473. PMID 12737575.
^ Allemand PM, Khemani KC, Koch A, et al. (1991). "Organic Molecular Soft Ferromagnetism in a Fullerene". Science. 253 (5017): 301–302. Bibcode:1991Sci...253..301A. doi:10.1126/science.253.5017.301. PMID 17794696. S2CID 19561675.
^ ^a ^b Bock, Hans; Borrmann, Horst; Havlas, Zdenek; et al. (1991). "Tetrakis(dimethylamino)ethene: An Extremely Electron-Rich Molecule with Unusual Structure both in the Crystal and in the Gas Phase". Angewandte Chemie International Edition in English. 30 (12): 1678–1681. doi:10.1002/anie.199116781.
^ H. Weingarten; W.A. White (1966), "Synthesis of Tetrakis(dimethylamino)ethylene", J. Org. Chem., vol. 31, no. 10, pp. 3427–3428, doi:10.1021/jo01348a520
^ US 3293299, H. Boden, "Process for making tetrakis(dimethylamino)ethylene", published 1966-12-20, assigned to E.I. du Pont de Nemours and Co.

[1] Spitz, Cédric; Terme, Thierry; Vanelle, Patrice (2023). "1,1,2,2-Tetrakis(dimethylamino)ethene". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X. hdl:10261/236866. ISBN 978-0-471-93623-7.

[2] David M. Lemal (1968). "Tetraaminoethylenes". In Saul Patai (ed.). The Amino Group. Patai's Chemistry of Functional Groups. pp. 701–748. doi:10.1002/9780470771082. ISBN 9780470771082.

[3] H.E. Winberg; J.R. Downing; D.D. Coffman (1965), "The Chemiluminescence of Tetrakis(dimethylamino)ethylene", J. Am. Chem. Soc., vol. 87, no. 9, pp. 2054–2055, doi:10.1021/ja01087a039

[4] "Chemilumineszenz von TDAE" (in German). illumina-chemie.de. 2014-08-08. Retrieved 2016-08-22.

[5] H.E. Winberg; J. R. Downing; D. D. Coffman (1965). "The Chemiluminescence of Tetrakis(dimethylamino)ethylene". J. Am. Chem. Soc. 87 (9): 2054–2055. doi:10.1021/ja01087a039.

[6] Broggi, Julie; Terme, Thierry; Vanelle, Patrice (2014-01-07). "Organic Electron Donors as Powerful Single-Electron Reducing Agents in Organic Synthesis" (PDF). Angewandte Chemie International Edition. 53 (2): 384–413. doi:10.1002/anie.201209060. PMID 24273111.

[7] Kuroboshi, Manabu; Waki, Yoko; Tanaka, Hideo (2003). "Palladium-Catalyzed Tetrakis(dimethylamino)ethylene-Promoted Reductive Coupling of Aryl Halides". The Journal of Organic Chemistry. 68 (10): 3938–3942. doi:10.1021/jo0207473. PMID 12737575.

[8] Allemand PM, Khemani KC, Koch A, et al. (1991). "Organic Molecular Soft Ferromagnetism in a Fullerene". Science. 253 (5017): 301–302. Bibcode:1991Sci...253..301A. doi:10.1126/science.253.5017.301. PMID 17794696. S2CID 19561675.

[Bock-9] Bock, Hans; Borrmann, Horst; Havlas, Zdenek; et al. (1991). "Tetrakis(dimethylamino)ethene: An Extremely Electron-Rich Molecule with Unusual Structure both in the Crystal and in the Gas Phase". Angewandte Chemie International Edition in English. 30 (12): 1678–1681. doi:10.1002/anie.199116781.

[10] H. Weingarten; W.A. White (1966), "Synthesis of Tetrakis(dimethylamino)ethylene", J. Org. Chem., vol. 31, no. 10, pp. 3427–3428, doi:10.1021/jo01348a520

[11] US 3293299, H. Boden, "Process for making tetrakis(dimethylamino)ethylene", published 1966-12-20, assigned to E.I. du Pont de Nemours and Co.

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