1-(Dimethylamino)-2-nitroethylene1

[1190-92-7]  · C4H8N2O2  · 1-(Dimethylamino)-2-nitroethylene  · (MW 116.14)

(synthetic reagent for nitroalkenes and nitroaromatics;1 can undergo addition-elimination reaction with nucleophiles;1 can effect inverse electron demand Diels-Alder reaction2)

Physical Data: mp 104 °C.

Solubility: sol alcohols, ethers, chloroform, acetone; slightly sol n-hexane.

Preparative Methods: by reaction of N,N-Dimethylformamide Diethyl Acetal (85% yield)3 or N,N-Dimethylformamide-Dimethyl Sulfate complex (60%)4 with Nitromethane; condensation of Triethyl Orthoformate with MeNO2 in the presence of DMF (52%),5 or addition-elimination reaction of 1-Nitro-2-phenylthioethylene with Me2NH (74%).6

Preparation of Nitroalkenes.

1-Dimethylamino-2-nitroethylene can be converted into synthetically useful nitroalkenes by addition-elimination reactions with nucleophiles such as organometallic reagents (eq 1),7 enolates (eq 2),8 indoles (eq 3),9 polyalkoxybenzenes (eq 4),9 a certain pyrimidine derivative (eq 5),10 and the anion of fluorene (eq 6).11

Preparation of Nitroaromatics.

Certain nitroalkene intermediates formed by addition-elimination reaction with active methylene compounds further undergo ring closure to produce nitroaromatics (eqs 7-9).12-14

3-Aryl-1,2,4,5-tetrazines react with 1-dimethylamino-2-nitroethylene by an inverse electron demand Diels-Alder reaction to give 3-aryl-5-nitropyridazines (eq 10).2

Related Reagents.

1-Nitro-2-phenylsulfonylethylene; 1-Nitro-2-phenylthioethylene.


1. (a) Rajappa, S. T 1981, 37, 1453. (b) Barrett, A. G. M.; Graboski, G. G. CRV 1986, 86, 751.
2. Marcelis, A. T. M.; van der Plas, H. C. H 1985, 23, 683.
3. Meerwein, H.; Florian, W.; Schön, N.; Stopp, G. LA 1961, 641, 1.
4. Severin, T.; Brück, B. CB 1965, 98, 3847.
5. Faulques, M.; Rene, L.; Royer, R. S 1982, 260.
6. Kamimura, A.; Ono, N. S 1988, 921.
7. Severin, T.; Scheel, D.; Adhikary, P. CB 1969, 102, 2966.
8. (a) Node, M.; Nagasawa, H.; Naniwa, Y.; Fuji, K. S 1987, 729. (b) Lerche, H.; König, D.; Severin, T. CB 1974, 107, 1509.
9. (a) Büchi, G.; Mak, C.-P. JOC 1977, 42, 1784. (b) Somei, M.; Sato, H.; Komura, N.; Kaneko, C. H 1985, 23, 1101.
10. Molina, P.; Vilaplana, M. J. S 1990, 474.
11. Severin, T.; Schnabel, I. CB 1969, 102, 1707.
12. Severin, T.; Brück, B.; Adhikary, P. CB 1966, 99, 3097.
13. Schäfer, H.; Gewald, K. ZC 1983, 23, 179.
14. Severin, T.; Adhikary, P.; Dehmel, E.; Eberhard, I. CB 1971, 104, 2856.

Rui Tamura

Ehime University, Matsuyama, Japan



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