[3156-70-5]  · C3H5NO2  · 1-Nitro-1-propene  · (MW 87.09)

(Michael addition of various nucleophiles such as organolithium reagents,5,6 enamines,13,15,19 allylstannane,9 and alkyl radicals22)

Physical Data: bp 58 °C/35 mmHg, 54 °C/28mmHg.

Solubility: sol THF, Et2O, acetone, CH2Cl2, toluene.

Analysis of Reagent Purity: IR: 1655, 1520 cm-1; NMR: d 1.95 (d, 3H, J = 6Hz), 6.83-7.55 (m, 2H).

Preparative Methods: dehydration of 1-nitro-2-propanol with Methanesulfonyl Chloride and Triethylamine (30% yield),2 Acetic Anhydride-AcONa (85% yield),3 or phthalic anhydride (55% yield).4

Handling, Storage, and Precautions: see 2-Nitro-1-propene.

Michael Acceptor.

1-Nitropropene is a useful reagent as a Michael acceptor for the addition of various nucleophiles (eq 1) including amines,1 alcohols,1 thiols,1 organolithium reagents (eqs 2 and 35,6), Grignard reagents,7 enamines,8 allylstannanes (eq 4),9 and lithium trialkylalkynylborates.10 Other organometallic reagents such as organoaluminum compounds11 and zinc-copper reagents RCu(CN)ZnI12 are also good candidates as nucleophiles.

Formaldehyde dimethylhydrazone readily adds to 1-nitropropene in the absence of base, giving the b-nitrodimethylhydrazone, which is converted into the b-nitroaldehyde by ozonolysis (eq 5).13

The Michael addition of 1,3-diketone dianions or 2-aminoenones to 1-nitropropene and subsequent aldol reaction (eqs 6, 7 and 814,15,16) provides a useful strategy for organic synthesis. In addition 1-nitropropene is an efficient reagent for bicycloannulation, as illustrated in eq 7.17

Allyl alcohols are prepared by the reaction of 1-nitropropene with thiols and aldehydes followed by reductive elimination of b-nitro sulfides with Tri-n-butylstannane (eq 9).16

As the addition of enolates18 or enamines19 to 1-nitropropene proceeds in a stereoselective way, asymmetric Michael addition is possible using chiral enolates (eq 10)20 or the titanated bislactim ether of cyclo(L-Val-Gly) (eq 11).21

1-Nitropropene reacts with alkyl radicals derived from O-acyl 2-thiopyridylhydroxamate to from new carbon-carbon bonds (eq 12).22

Diels-Alder Reaction.

1-Nitropropene is a very reactive dienophile in the Diels-Alder reaction, and the regiochemistry is controlled by the nitro group (eq 13).23

Related Reagents.

Nitroethylene; 2-Nitro-1-propene.

1. (a) Schickh, O.; Apel, G.; Padeken, H. G.; Schwartz, H. H.; Segnitz, A. MOC 1971, 10, 9-462. (b) Barrett, A. G. M.; Graboski, G. G. CRV 1986, 86, 751. (c) Seebach, D.; Colvin, E. W.; Lehr, F.; Weller, T. C 1979, 33, 1. (d) Rossini, G.; Ballini, R. S 1988, 833. (e) Baer, H.; Urbas, L. The Chemistry of the Nitro and Nitroso Groups; Feuer, H., Ed.; Interscience: New York, 1970; Part 2, pp 75-200. (f) Tamura, R.; Kamimura, A.; Ono, N. S 1991, 423.
2. Melton, J.; McMurry, J. E. JOC 1975, 40, 2138.
3. Mauny, H. C. BSF 1940, 7, 133.
4. Buckley, G. D.; Scaife, C. W. JCS 1947, 1471.
5. Seebach, D.; Leitz, H. F.; Ehrig, V. CB 1975, 108, 1924.
6. Ghera, E.; Ben-Yaakov, B.; Yechezkel, T.; Hassner, A. TL 1992, 33, 2741.
7. (a) Buckley, D. G. JCS 1947, 1494. (b) Buckley, D. G.; Ellery, E. JCS, 1947, 1497.
8. Felluga, F.; Nitti, P.; Pitacco, G.: Valentin, E. JCS(P1) 1992, 2331.
9. Yamamoto, Y.; Nishii, S. JOC 1988, 53, 3597.
10. Pelter, A.; Hughes, L.; Rao, J. M. JCS(P1) 1982, 719.
11. Pecunioso, A.; Menicagli, R. JOC 1989, 54, 2391.
12. Jubert, C.; Knochel, P. JOC 1992, 57, 5431.
13. Lassaletta, J. M.; Fernandez, R. TL 1992, 33, 3691.
14. Ehrig, V.; Seebach, D. CB 1975, 108, 1961.
15. Felluga, F.; Nitti, P.; Pitacco, G.; Valentin, E. JCS(P1) 1991, 1645.
16. Ono, N.; Kamimura, A.; Kaji, A. TL 1984, 25, 5319.
17. Cory, R. M.; Anderson, P. C.; McLaren, F. R.; Yamamoto, B. R. CC 1981, 73.
18. Häner, R.; Laube, T.; Seebach, D. C 1984, 38, 255.
19. Seebach, D.; Beck, A. K.; Golinski, J.; Hay, J. N.; Laube, T. HCA 1985, 68, 162.
20. Calderari, G.; Seebach, D. HCA 1985, 68, 1592.
21. Busch, K.; Groth, U. M.; Kühnle, W.; Schölkopf, U. T 1992, 48, 5607.
22. Sumi, K. D.; Fabio, R.; Hanessian, S. TL 1992, 33, 749.
23. (a) Drake, N. L.; Ross, A. B. JOC 1958, 23, 717. (b) Ono, N.; Miyake, H.; Kamimura, A.; Kaji, A. JCS(P1) 1987, 1929.

Noboru Ono

Ehime University, Matsuyama, Japan

Copyright 1995-2000 by John Wiley & Sons, Ltd. All rights reserved.