1
78 Letters in Organic Chemistry, 2009, Vol. 6, No. 2
Brinchi et al.
and H
2
O
2
as environmentally benign oxidant: short reaction
(t, 2 H, CH
ꢂ = 0.82 (t, 3 H, ꢃꢁCH
2H, CH -CH -CO), 2.1 ( t, 2 H, CH
CH -(CH ꢁCOꢁNH
(m, 2H, CH -CH -CH
2
-CO), 5.3 (b, 2H, NH
), 1.19-1.23 (m, 8H, chain), 1.5 (b,
-CO), 5.3 (b, 2H, NH ).
: ꢂ = 0.82 (t, 3 H, ꢃꢁCH ), 1.25-1.36
-CO), 1.53-1.68 (m, 2H, CH
-CO), 5.3 (b, 2H, NH
: ꢂ = 1.17 (s, 9 H, CH
ꢁCOꢁNH : ꢂ = 2.48 (t, 2 H, CH
-CH -CO), 7.14-7.27 (m, 5H, Ar), 5.3 (b,
). (cyclohex-1-en-1-yl)-CH ꢁCOꢁNH : ꢂ = 1.48-
.64 (m, 4H, CH -CH ), 1.94-1.98 (m, 4H, CH -CH=C-
), 2.8 (s, 2H, CH -CO), 5.2-5.5 (d, 2H, NH ), 5.6 (s, 1H,
CH=C-). PhꢁCOꢁNH : ꢂ = 7.35-7.48 (m, 3H, Ar), 7.73-
.78 (m, 2H, Ar). 2-Me-PhꢁCOꢁNH : ꢂ = 2.45 (s, 3 H,
), 7.15-7.41 (m, 4H, Ar), 5.6 (b, 2H, NH ). 3-NH
: ꢂ = 5.0 (b, 2H, Ar-NH ), 5.6 (b, 2H, NH
.9 (m, 1H, Ar), 7.3-7.6 (m, 3H, Ar). 4-NO -PhꢁCOꢁNH
ꢂ = 8.10 (d, 2H, Ar), 8.27 (d, 2H, Ar), 5.9 (b, 2H, NH ). 4-
Cl-Ph-CH ꢁCOꢁNH : ꢂ = 3.50 (s, 2 H, CH CO), 7.14-7.20
m, 2H, Ar), 7.29 (d, 2H, Ar), 5.3 (b, 2H, NH ). Ph-
CO), 7.20-7.36 (m,
). PhꢁCH(CH )ꢁCOꢁNH : ꢂ =
), 3.49-3.60 (m, 1 H, CHCO), 7.21-7.31 (m,
H, Ar), 5.3 (b, 2H, NH ).
2 3 2 6 2
). CH -(CH ) ꢁCOꢁNH :
time, high selectivity, mild reaction conditions, easy isola-
tion of high yields of pure products. Recycle of aqueous sur-
factant solution was possible. Scale up to a practical scale,
was also tried and the methodology was still good using up
to 5 g of reagent dodecanenitrile.
3
2
2
2
2
3
2
)
3
2
3
2
2
2
2
-CH
2
-
).
CO), 2.1 ( t, 2 H, CH
CH CꢁCOꢁNH
NH ). Ph-CH CH
.92 (t, 2H, CH
H, NH
2
2
(
3
)
3
2
3
), 5.4 (b, 2H,
CO),
2
2
2
2
2
EXPERIMENTAL
General Remarks
2
2
1
2
2
2
2
2
2
2
2
The preparation and purification of surfactants has been
described previously [8]. Nitriles were from Aldrich and
used without further purification. H-NMR were measured
CH
2
2
2
1
2
7
2
3
on a 200 MHz FT Bruker instrument, in CDCl , and chemi-
CH
3
2
2
-
cal shifts are relative to internal TMS. Melting points were
measured with a Büchi 510 melting point apparatus and are
uncorrected.
PhꢁCOꢁNH
2
2
2
),
6
2
2
:
2
2
2
2
(
2
Reaction Conditions
2 2 2
CH ꢁCOꢁNH : ꢂ = 3.53 (s, 2 H, CH
As a typical procedure nitrile (1 mmol) was solubilized in
5
1
5
H, Ar), 5.3 (b, 2H, NH
.48 (d, 3 H, CH
2
3
2
2
0 ml aqueous basic surfactant solution ([CTAOMs] = 0.05
3
M, [NaOH] = 0.1 M) and then a 5-fold excess of hydrogen
peroxide was added as a 30 % solution (0.6 ml) under mag-
netic stirring, at 25°C. The resulting mixture was stirred at
2
2
5°C. After the reaction time, the mixture was extracted into
ACKNOWLEDGEMENT
EtOAc (2ꢀ20 ml), with no emulsion formation. Combined
extracts were washed, first with sodium bicarbonate solution,
to remove any trace of acid, then with brine until neutrality,
Support of this work by Ministero dell’Università e
Ricerca, (MUR) Rome, is gratefully acknowledged.
2 4
and dried over anhydrous Na SO . The solvent was thereaf-
ter evaporated under reduced controlled pressure at 50°C to
give the crude solid product, that was treated with petroleum
ether, warmed and then cooled to 0°C; the solid was then
filtered, and dried again and again until a constant weight to
give the pure amide. The amide was weighted to calculate
the yield.
REFERENCES
[
[
1]
2]
Li, C.J. Chem. Rev., 1993, 93, 2023.
Adams, D.J.; Dyson, P.J.; Tavener, S.J. Chemistry in Alternative
Reaction Media, Wiley: Cheichester, 2004.
[3]
Grieco, P.A. Ed.; Organic Synthesis in Water, Blacky Academic
and Professionals: London, 1998.
[4]
(a) Anastas, P.T.; Warner, J.C. Green Chemistry: Theory and Prac-
tice; Oxford University Press: Oxford, 1998. (b) Anastas, P.T.; Kir-
choff, M.K. Acc. Chem. Res., 2002, 35, 686. (c) Trost, B.M. Acc.
Chem. Res., 2002, 35, 695.
For the recycle, after extraction of the product with ethyl
ether (2ꢀ 20 ml), the aqueous surfactant solution was kept
under reduced pressure (500 mmHg) at 40°C to remove any
trace of ethyl ether, and then the reagents (dodecanenitrile
and hydrogen peroxide) were added to this aqueous solution,
as described previously.
[5]
Fendler, J.H. Membrane Mimetic Chemistry; Wiley: New York,
1
982.
(a) Bunton, C.A.; Savelli, G. Adv. Phys. Org. Chem., 1986, 22,
31; (b) Savelli, G.; Germani, R.; Brinchi, L. in Reactions and Syn-
[6]
2
thesis in Surfactant Systems; Texter, J., Ed.; Dekker: New York,
2001; Vol. 100, pp. 175-246; (c) Khan, M.N. Micellar Catalysis, In
Surfactant Science Series, ed. CRC/ Taylor& Francis: New York,
For the scale-up of the procedure 1g (5.5 mmol) or 5g
(
28 mmol) of dodecanenitrile were introduced in a 500 ml
2
006, Vol. 133.
round-bottom flask in 50 ml aqueous basic surfactant solu-
tion ([CTAOMs] = 0.05 M, [NaOH] = 0.1 M). The nitrile
does not solubilize completely. Hydrogen peroxide was
added in 5-fold excess as a 30% solution under magnetic
stirring at 25°C. Gas (O ) evolves during the reaction with
2
huge amounts of foam production. Further work-up is as
already described.
[
7]
8]
Holmberg, K. Adv. Colloid Interface Sci., 1994, 51, 137; (b) Tas-
cioglu, S. Tetrahedron, 1996, 52, 11113; (c) Dwars, T.; Paetzold,
E.; Oehme, G. Angew. Chem. Int. Ed., 2005, 44, 7174.
Aramini, A.; Brinchi, L.; Germani, R.; Savelli, G. Eur. J. Org.
Chem., 2000, 1793; (b) Brinchi, L.; Di Profio, P.; Germani, R.;
Savelli, G.; Bunton, C.A. Colloid Surface A, 1998, 132, 303. (c)
Biondini, D.; Brinchi, L.; Germani, R.; Goracci, L.; Savelli, G. Eur.
J. Org. Chem., 2005, 3060.
[
[9]
(a) Beckwith, A.L.J. in The Chemistry of Amides: Synthesis of
Amides, Zabicky, J., Ed.; Interscience: New York, 1970, pp. 73186.
(b) Schaefer, F.C. In The Chemistry of the Cyano Group: Nitrile
Reactivity, Rappoport Z., Ed.; Interscience: New York, 1970, pp.
239-306.
Product Characterization
The structures and purity of the amides were confirmed
1
[
[
10]
11]
Kim, J.H.; Britten, J.; Chin, J. J. Am. Chem. Soc., 1993, 115, 3618.
Koffl-Bie Djoman, M.C.; Nalt, Ajjou, A. Tetrahedron Lett., 2000,
by H-NMR and m.p. of amides, agreeing with literature
ones [21, 23].
4
1, 4845.
1
[12]
(a) Rao, C.G. Synth. Commun., 1982, 12, 177; (b) Liu, K.T. Synthe-
sis, 1988, 715; (c) Khadilkar, B.M.; Madyar, V.R. Synth. Commun.,
H-NMR (200 MHz, CDCl
-(CH 10ꢁCOꢁNH : ꢂ = 0.82 (t, 3 H, ꢃ-CH
.14-1.19 (m, 16H, chain), 1.5(b, 2H, CH -CH -CO), 2.1
3
, r.t.) of various amides fol-
low: CH
3
2
)
2
3
),
2
002, 32, 1731.
1
2
2