ZINCDIMETHYLFORMAMIDE

ZincDimethylformamide1

of some of the products formed from gem-dibromocyclopropanes

were comparable to those obtained by other methods.
Br

Zn Me2NCHO

Br

Br

Zn, DMF

(3)

60%

(Zn)

[7440-66-6]
Zn
(MW 65.39)
InChI = 1/Zn
InChIKey = HCHKCACWOHOZIP-UHFFFAOYAS
(DMF)
(MW 73.11)
[68-12-2]
C3 H7 NO
InChI = 1/C3H7NO/c1-4(2)3-5/h3H,1-2H3
InChIKey = ZMXDDKWLCZADIW-UHFFFAOYAS

Zn, DMF

Br

Br
Br

g cm3 ;

Reduction of Halides. The first use of a mixture of zinc and

DMF as a dehalogenating reagent was employed by Alder and
Fremery in 1961.1 In a study of formation of ortho biradicals,
they employed Zn/DMF to reduce , -dibromoxylene (eq 1)
which generated unstable 5,6-dimethylene-1,3-cyclohexadiene.
This diene undergoes a DielsAlder reaction with dienophiles
like Acrylonitrile, Acrolein, and Ethyl Acrylate in high yield. A
similar reaction has also been employed in the dimethylenecyclooctatriene system.2
CN

Zn

DMF: bp
d 7.140
Physical Data: zinc: mp
153 C; d 0.944 g cm3 .
Solubility: sol DMF, THF, Et2 O, toluene, alcohol.
Preparative Methods: see text.
Handling, Storage, and Precautions: see Zinc and N,N-Dimethylformamide.

Br
Br

(4)

58%

Br

(reducing agent for halides,3 azides,10 and aldehydes11 )

419.5 C;

DMF

Br

30%

13%

O
O

1. Zn, DMF

N3
O

2. Ac2O, EtOH

95%

(1)

O
O

A systematic study of Zn/DMF as a dehalogenating reagent was

investigated by Mehta and Kapoor.3 It was found that ordinary
zinc powder reacts with a variety of alkyl halides in DMF
to furnish the corresponding organozinc compounds. Aqueous
decomposition of these solutions gave the expected hydrocarbons in good yield. The procedure is a satisfactory alternative for dehalogenation when the commonly employed hydride
complexes4 or metal amines5 cannot be used. For example, 8,15dibromolongibornan-9-one was reduced to longibornan-9-one in
82% yield using Zn/DMF (eq 2).
O

95100 C
82%

25%

Reduction of Azides. Carbohydrate azides are valuable intermediates for the synthesis of amino sugars. This transformation is
commonly brought about by catalytic reduction.7 or by treatment
with Lithium Aluminum Hydride8 or Sodium Borohydride9
Ohrui and Emoto discovered that Zn/aq DMF is an excellent
reagent to reduce an azide group to the corresponding amine group
(eq 6).10 This reaction was complete in 45 min whereas the corresponding sodium borohydride reduction required 2030 h.

DMF

Zn, DMF

(5)

CN

Zn

80%

Br

O
NHAc
O

(6)
O

Reduction of Aldehydes to Alcohols. A mixture of Zn

and Antimony(III) Chloride in aqueous DMF reduces aldehydes
to the corresponding alcohols in excellent yield.11 A variety
of aliphatic (eq 7), aromatic (eq 8), and ,-unsaturated
(eq 9) aldehydes were reduced to alcohols under relatively mild
conditions.
SbCl3, Zn

CHO

(2)

OH

aq DMF
95%

(7)

Br
CHO

In a subsequent study, reaction of dibromocyclopropane with

Zn/DMF gave monobromocyclopropane (eq 3), allene (eq 4), or
a mixture of products (eq 5), depending on the ring system of
the substrate.6 Thus no generalization could be made. The yields

CH2OH
SbCl3, Zn

(8)

aq DMF
90%

Cl

Cl
Avoid Skin Contact with All Reagents

ZINCDIMETHYLFORMAMIDE

SbCl3, Zn

OHC

aq DMF
96%

(9)
HO

1. Alder, K.; Fremery, M., Tetrahedron 1961, 14, 190.

2. Elix, J. A.; Sargent, M. V.; Sondheimer, F., J. Am. Chem. Soc. 1970, 92,
962.
3. Mehta, G.; Kapoor, S. K., J. Organomet. Chem. 1974, C33.
4. Gaylord, N. G. Reduction with Complex Metal Hydrides; Wiley: New
York, 1956.

A list of General Abbreviations appears on the front Endpapers

5. House, H. O. Modern Synthetic Reactions; Benjamin: New York, 1965.

6. Mehta, G.; Kapoor, S., J. Organomet. Chem. 1974, 213.
7. Dick, A. J.; Jones, J. K. N., Can. J. Chem. 1965, 43, 977.
8. Clophax, J.; Gro, S. D.; Hildesheim, J., J. Chem. Soc., Chem. Commun.
1968, 94.
9. (a) Boyer, J. H.; Ellzey, S. E., J. Org. Chem. 1958, 23, 127. (b) Ali, Y.;
Richardson, A. C., Carbohydr. Res. 1967, 5, 441.
10. Ohrui, H.; Emoto, S., Carbohydr. Res. 1969, 10, 221.
11. Wang, W. B.; Shi, L. L.; Huang, Y. Z., Tetrahedron Lett. 1990, 31,
1185.

Hemantkumar H. Patel
Abbott Laboratories, North Chicago, IL, USA