Glyoxal Diethyl Acetal

(1; R = Et)

[5344-23-0]  · C6H12O3  · Glyoxal Diethyl Acetal  · (MW 132.16) (2; R = Me)

[51673-84-8]  · C4H8O3  · Glyoxal Dimethyl Acetal  · (MW 104.11)

(reagents for preparation of a,b-unsaturated aldehydes1-8 and heterocyclic compounds1,9-12)

Alternate Name: diethoxyacetaldehyde.

Physical Data: (1) bp 50-55 °C/10 mmHg; (2) bp 60-90 °C/150 mmHg.

Form Supplied in: liquids; commercially available.

Preparative Methods: preparations usually involve either oxidative cleavage of glyceraldehyde acetals,12-15 or reductive ozonolysis of acrolein5,16 or crotonaldehyde1 dialkyl acetals. Three new preparative procedures were recently reported.17-19

Handling, Storage, and Precautions: these compounds are moisture sensitive. They should be stored under inert gas and at low temperature.

Wittig Reactions.

Wittig or Horner-Emmons reactions yield a,b-ethylenic acetals.1-8,10,14 Subsequent deacetalization, usually by moist silica gel, gives a,b-ethylenic aldehydes.1-8 This approach was used in the synthesis of ethyl (2E,4Z)-decadienoate, a natural product from Pyrus communis, in which two of the three steps are Horner-Emmons reactions with dimethoxy- or diethoxyacetaldehyde and then deacetalization20 (eqs 1-4).3-5,8

Synthesis of Heterocyclic Compounds.

Synthesis of complex alkaloids9 and 4-methoxycarbonyl-a-pyrone (eq 5)1 are based on successive reactions towards both functions of diethoxy-9 or dimethoxyacetaldehyde.1 Another possibility is the formation of heterocyclic compounds bearing an acetal function.10-12 For instance, the Pictet-Spengler reaction between tryptophan derivatives and diethoxyacetaldehyde gives substituted tetrahydro-b-carbolines (eq 6).11

Reactions with Nucleophiles.

Organomagnesium18a,21 and organolithium17,22 compounds as well as metal hydrides18a lead to the expected acyloin acetals. As mentioned above, reaction of nitrogen compounds often leads to heterocyclic compounds; however, there are various other interesting possibilities.18a,23 For instance, a novel synthesis of a-aminoaldehydes involves a substitution reaction between organomagnesium compounds and products obtained from benzotriazole, diethoxyacetaldehyde, and primary or secondary amines (eq 7).23d

Other Reactions.

Dialkoxyacetaldehydes are also reagents for preparation of 1,4-dicarbonyl compounds16 and of chiral a-hydrazono acetals.24

Related Reagents.

Pyruvaldehyde Diethyl Acetal; Ethyl Diethoxyacetate; Ethyl 3,3-Diethoxypropanoate; Ethyl Lithioacetate; Glyoxal; Methyl Glyoxylate.


1. Haneda, A.; Uenakai, H.; Imagawa, T.; Kawanisi, M. SC 1976, 141.
2. Bonjouklian, R.; Ruden, R. A. JOC 1977, 42, 4095.
3. Pellet, M.; Huet, F.; Conia, J. M. JCR(S) 1982, 248 JCR(M) 1982, 2552.
4. Lechevallier, A.; Huet, F.; Conia, J. M. T 1983, 39, 3307 (CA 1983, 100, 120 544k).
5. Bestmann, H. J.; Ermann, P. CB 1983, 116, 3264 (CA 1983, 99, 157 939e).
6. Wickham, G.; Wells, G. J.; Waykole, L.; Paquette, L. A. JOC 1985, 50, 3485.
7. Bestmann, H. J.; Ermann, P.; Rueppel, H.; Sperling, W. LA 1986, 479 (CA 1986, 105, 60 777e).
8. Pinsard, P.; Lellouche, J. P.; Beaucourt, J. P.; Toupet, L.; Schio, L.; Gree, R. JOM 1989, 371, 219.
9. Battersby, A. R.; Stauton, J.; Wiltshire, H. R.; Bircher, B. J.; Fuganti, C. JCS(P1) 1975, 1162.
10. Lassalle, G.; Gree, R.; Toupet, L. BSF(2) 1990, 453 (CA 1991, 114, 143 036z).
11. Ungemach, F.; Di Pierro, M.; Weber, R.; Cook, J. M. JOC 1981, 46, 164 and refs. therein.
12. Lehn, J. M.; Regnouf de Vains, J. B. HCA 1992, 75, 1221.
13. Fisher, H. O. L.; Baer, E. HCA 1935, 18, 514 (CA 1935, 29, 5075-7).
14. Meyers, A. I.; Nolen, R. L.; Collington, E. W.; Narwid, T. A.; Strickland, R. C. JOC 1973, 38, 1974.
15. Battersby, A. R.; Staunton, J.; Wiltshire, H. R. JCS(P1) 1975, 1162.
16. Stetter, H.; Mohrmann, K. H. S 1981, 129 (CA 1981, 94, 174 238q).
17. Bernard, D.; Doutheau, A.; Gore, J. SC 1987, 17, 1807.
18. Hamedi-Sangsari, F.; Chastrette, F.; Chastrette, M. SC 1988, 1343.
19. Babler, J. H. SC 1987, 17, 77.
20. Stambouli, A.; Amouroux, R.; Chastrette, M. TL 1987, 28, 5301 (CA 1988, 109, 6082u).
21. Birkofer, L.; Wundram, D. CB 1982, 115, 1132 (CA 1982, 96, 199 775s).
22. Maier, S.; Preuss, R.; Schmidt, R. R. LA 1990, 483 (CA 1990, 113, 24 417u).
23. (a) Corey, E. J.; Kang, M.-C.; Desai, M. C.; Ghosh, A. K.; Houpis, I. N. JACS 1988, 110, 649. (b) Smith, M. J. TL 1989, 30, 313. (c) Afarinkia, K.; Rees, C. W.; Cadogan, J. I. G. T 1990, 46, 7175; (d) Katritzky, A. R.; Borowiecka, J.; Fan, W.-Q. S 1990, 1173.
24. Thiam, M.; Chastrette, F. BSF(2) 1992, 161 (CA 1992, 117, 131 133c).

François Huet

University of Le Mans, France



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