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(versatile reagent for reduction of aldehydes, ketones, unsaturated conjugated ketones, '
quinones, diunsaturated acids, azo, nitro, and nitroso compounds, ' imines, oximes,
tropylium salts, pyridinium salts, pyrazine, and vinyl sulfones; ;~ intramolecular Marschalk
cyclizations, , dehalogenation of vic dibromides and a-halo ketones, Claisen rearrangement of
allyloxyanthraquinones and for the synthesis of 8-arylaminopurines ' )
Preparative Methods: by the action of Sulfur Dioxide on Sodium Amalgam in alcoholic solution.
stereoselectivity similar to that obtained with metal hydrides (Sodium Borohydride) and opposite to dissolving
metals reductions, e.g. the reductions of3a.-hydroxy-7-keto-5~-cholanic acid to diols (eq 1).
\
\
\
..
H
\
+ (1)
N~ 100% 85:15
K,100% 94:6
Na2S204,100% 4:96
NaBH4,100% 6:94
(2)
91%
65%
° (3)
.. (4)
63%
\
Quinones to Hydroquinones.
Most Quinones are reduced by sodium dithionite to hydroquinones. Naphthacenequinone and higher linear
benzologs are exceptional in that they are not reduced by alkaline sodium dithionite. Sodium dithionite reduces
anthraquinone to anthrone.
NaOH
..
74% 2%
Azo to Amine.
Azobenzene is reduced to aniline by sodium dithionite. This reaction is used to introduce an amino group into a
phenolic compound by first coupling with an aromatic diazonium salt and then reducing the resulting hydroxyazo
derivatives with N~S204' e.g. 2- and 4-amino-I-naphthols can be prepared from I-naphthol.
Nitro to Amine.
Various aromatic nitro compounds are reduced conveniently to the corresponding aniline<krivatives with sodium
dithionite using dioctyl viologen as an electron-transfer catalyst in a two-phase system (CH2CI2-H20), e.g. 1-
nitronaphthalene to 1-naphthylamine.
Nitroso to A"mine.
Nitroso compounds are reduced to amines by sodium dithionite, e.g. nitrosouracil to diaminouracil (eq 6).
Reduction of N-nitrosodibenzylamine with N~S204 is accompanied by liberation ofN2 and rearrangement to
dibenzyl. Mixed benzylaryl or diaryl-N-nitrosoamines are reduced to hydrazines (eq 7).
NH2
\ ... (6)
68-81%
NO NH2
OR OH
• (7)
Imines to Amines.
Sodium dithionite in DMF reduces imines to N-alkylamines at 110°C with yields ranging from 40 to 73%.
Heating N-cyclohexyldibenzylamine, sodium dithionite, and NaHC0 3 in DMF for 30 min at 110°C gives 73%
benzylcyclohexylamine.
Oximes to Amines.
Oximes are readily reduced to amines by sodium dithionite. Substituted phenylethylamines are key intermediates
required for the synthesis of isoquinoline derivatives. They are readily obtained from aryl alkyl ketones by
nitrosation of the alkyl group followed by the reduction of the resulting oxime derivatives by sodium dithionite (eq
8). .l'
o ".
.. Ph~ (8)
NH2
Cleavage of Oximes.
Both aldehydes and ketones are regenerated from their oxime derivatives with aqueous sodium dithionite either
alone or in the presence ofN~C03 at 25°C, e.g. cyclohexanone oxime to cyclohexanone (95%) and benzaldehyde
oxime to benzaldehyde (96%).
2 x-
MeCN
. (9)
. Ph
R
o\\110 R
Ph Ph
Na2S204 S
R X- ~ ...
(10)
Ph . Ph
R=H,Ph
C'ONH 2·
.. (11)
,I
.. , (13)
57%
(Z) 98%
OMe 0 OR
72%
.. (15)
o OH
Synthesis of 8-Arylaminotheophyllines.
Treatment of 5-arylazo-l,3-dimethyl-6-ethoxymethyleneaminouracil with N~S204 in formic acid gives 8-
arylaminotheophyllines (eq 16). The key intermediates required for this reaction are prepared by reaction of the
appropriate 6-amino-5-arylazo-l,3-dimethyluracils with a mixture of Triethyl Orthoformate and DMF at 180°C
for 5 h.
.,-
0 0
Me, N· Me,
N ~N Na2S204
.. N
(16)
oAN I
N~Et HC0 2H O~NI
Me "r Me
1. (a) FF1967, 1,1081; 1980,8,456; 1981,9,426; 1982,10,363; 1988,13,277. (b) Louis-Andre, 0.; Gelbard, G.
BSF(2) 1986, 565.
2. de Vries, J. G.; van Bergen, T. J.; Kellogg, R. M. S 1977, 246.
3. Camps, F.; ColI, J.; Riba, M. CC 1979, 1080.
4. House, H. O. Modern Synthetic Reactions, 2nd ed.; Benjamin/Cummings: London, 1972; p 150.
5. Castaldi, G.; Perdoncin, G.; Giordano, C.; Minisci, F. TL 1983, 24, 2487.
6. Giordano, C.; Perdoncin, G.; Castaldi, G. AG(E) 1985, 24, 499.
7. Camps, F.; ColI, J.; Guitart, J. T 1986, 42, 4603.
8. Louis-Andre, 0.; Gelbard, G. TL 1985, 26, 831.
9. Fieser, L. F. JACS 1931, 53, 2329.
10. Fieser, L. F.; Peters, M. A. JACS 1931, 53, 4080.
11. Camps, F.; ColI. J.; Guerrero, A.; Guitart, J.; Rib~ M. CL 1982, 715.
- 12. Fieser, L. F. OSC 1943, 2, 35, 430.
13. Park, K. K.; Oh, C. H.; Joung, W. K. TL 1993, 34, 7445.
14. Sherman, W. R.; Taylor, Jr., E. C. OSC 1963, 4, 247.
15. Overberger, C. G.; Lombardino, J. G.; Hiskey, R G. JACS 1958, 80, 3009.
16. Pojer, P. M. AJC 1979, 32, 201.
17. Pictet, A.; Gams, A. CB 1909, 42, 2943.
18. Weiss, R.; Schlierf, C.; Koelbl, H. TL 1973, 4827.
19. Mauzerall, D.; Westheimer, F. H. JACS 1955, 70,2261.
20. Mager, H. I. X.; Berends, W. RTC 1960, 79, 282.
~.
21. Julia, M.; Lauron, H.; Stacino, J.-P.; Verpeaux, J.-N.; Jeannin, Y.; Drornzee, Y. T1986, 42, 2475.
. 22. Suzuki, F.; Trenbeath, S.; Gleim, R. D.; Sih, C. J. JACS 1978, 100, 2272.
23. Kende, A. S.; Tsay, Y.-G.; Mills, J. E. JACS 1976, 98, 1967.
24. K.empe, I.; Norin, T.; Caputo, R. ACS 1976, B30, 366...
25. Chung, S.-K.; Hu, Q.-Y. SC 1982, 12,261. .
26. Boddy, I. K.; Boniface, P. J.; Cambie, R. C.; Craw, P. A.; Larsen, D. S.; McDonald, H.; Rutledge, P. S.;
Woodgate, P. D. TL 1982, 23, 4407. \I
27. Senga, K.; Ichiba, M.; Kanazawa, H.; Nishigaki, S.; Higuchi, M.; Yoneda, F. S 1977, 4, 264.
28. Senga, K.; Ichiba, M.; Kanazawa, H.; Nishigaki, S.; Higuchi, M.; Yoneda, F. JHC 1978, 15, 641.
29. Chia, K.-S; Wang, W.-P. -Union Ind Res. Inst. Report (Hsinchu, Taiwan), No. 40, 1959; p.1 (CA 1960,54,
19252g).
30. Chia, K.-S; Wang, W.-P. Chemistry (I'aipei) 1960, 29 (CA 1961, 55, 2327h).
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