Nitroaldol Reaction in Aqueous Media: An Important Improvement of the Henry Reaction

Full text of DOI:10.1021/jo961201h

J . Org. Chem. 1997, 62, 425-427
425
Nitr oa ld ol Rea ction in Aqu eou s Med ia : An
Sch em e 1
Im p or ta n t Im p r ovem en t of th e Hen r y
Rea ction
Roberto Ballini* and Giovanna Bosica
Dipartimento di Scienze Chimiche dell’Universit a` ,
Via S. Agostino n. 1, 62032 Camerino, Italy
procedures furnish a diastereomeric mixture of nitroal-
kanols; nevertheless, this seems to be not a problem since
the main uses of nitroalkanols are the conversion into
Received J une 25, 1996
R-nitro ketones1
c,8,10-12
or conjugated nitroalkenes,
which at least one stereogenic center is lost.
13-17
in
Carbon-carbon bond formation is the essence of or-
ganic synthesis; the Henry reaction, an aldol-type reac-
tion, represents one of the classical C-C bond-forming
processes, and its variants have been used extensively
in many important syntheses.1
If a diastereoselective synthesis of nitroalkanols, for
specific purposes, is required other procedures are avail-
-19
18
able; however, these methods are highly laborious and/
The classical nitroaldol reaction is performed, as
routine procedure, in presence of a base (Scheme 1) in
an organic solvent. Since basic reagents are also cata-
lysts for the aldol condensation and for the Cannizzaro
reaction when aldehydes are used as carbonyl sources,
it is necessary to adopt experimental conditions to
or produce low yields, are of moderate generality, and
are not suitable on a large scale.
The need to reduce the amount of toxic waste and
byproducts arising from chemical processes requires
increasing emphasis on the use of less toxic and envi-
ronmentally compatible materials in the design of new
5
-9,17,19
suppress these competitive reactions.
To obtain
21
synthetic methods. The time has now come for ecologi-
better yields of 2-nitro alcohols a careful control of the
basicity of the reaction medium is necessary, and long
reaction times are demanded. Furthermore, the â-ni-
troalkanols formed may undergo base-catalyzed elimina-
tion20 of water to give nitroalkenes that readily polymer-
ize. This elimination is difficult to avoid when aryl
aldehydes are employed. In addition, these standard
cal factors to be considered in the development of
synthetic procedures and for them to play an important
role in the assessment of the quality of any new synthe-
sis. Within this context, the reduced use of ecologically
suspected solvents is of considerable significance. In
recent years, there has been increasing recognition that
water is an attractive medium for many organic reac-
tions.22 The aqueous medium with respect to organic
solvent is less expensive, less dangerous, and environ-
ment-friendly, while it allows the control of the pH and
the use of microaggregates such as surfactants. Gener-
ally, the low solubility23 of most reagents in water is not
an obstacle to the reactivity, which, on the contrary, is
reduced with the use of cosolvents.
(
1) (a) Seebach, D.; Colvin, E. W.; Leher, F.; Weller, T. Chimia 1979,
3
3, 1-18. (b) Rosini, G. In Comprehensive Organic Synthesis; Trost,
B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 2, p 321. (c) Rosini,
G.; Ballini, R. Synthesis 1988, 833-847. (d) Rosini, G.; Ballini, R.;
Sorrenti, P. Synthesis 1983, 1014-1016.
(
2) Ballini, R.; Bosica, G.; Forconi, P. Tetrahedron 1996, 52, 1677-
1
684.
3) Sasai, H.; Suzuki, T.; Itoh, N.; Tanaka, K.; Date, T.; Okamura,
K.; Shibasaki, M. J . Am. Chem. Soc. 1993, 115, 10372-10373.
4) Kiyooka, S.; Tsutsui, T.; Maeda, H.; Kaneoko, Y.; Isobe, K.
(
(
In connection with our interest devoted to the synthe-
Tetrahedron Lett. 1995, 36, 6531-6534.
24
ses of natural products via R-nitro ketones or nitroalk-
(
(
(
5) Vaderbilt, B. M.; Hass, H. B. Ind. Eng. Chem. 1940, 32, 34-38.
6) Hass, H. B.; Riley, E. F. Chem. Rev. 1943, 32, 373-430.
7) Lichtenthaler, F. W. Angew. Chem., Int. Ed. Engl. 1964, 3, 211-
enes,25 we decided to investigate the possibility to achieve
the nitroaldol reaction in water. After some trials we
found that the Henry reaction can be performed under
very mild reaction conditions, in aqueous media, using a
stoichiometic amount of the nitroalkane 1 and the
aldehyde 2 in NaOH 0.025 M, in the presence of cetylt-
rimethylammonium chloride (CTACl) as cationic surfac-
tant. As showed in Table 1 the yields are from good to
excellent when the nitroalkanes react with aliphatic
aldehydes, while the yields slightly decrease with the
2
24.
(
8) M e´ lot, J .-M.; Texier-Boullet, F.; Foucaud, A. Tetrahedron Lett.
1
986, 27, 493.
(9) Costantino, V.; Curini, M.; Marmottini, F.; Rosati, O.; Pisani,
E. Chem. Lett. 1994, 2215.
(
(
10) Hurd, C. D.; Nilson, M. E. J . Org. Chem. 1955, 20, 927-936.
11) (a) Rosini, G.; Ballini, R. Synthesis 1983, 543-544. (b) Rosini,
G.; Ballini, R.; Sorrenti, P.; Petrini, M. Synthesis 1984, 607-608.
(
12) Rosini, G.; Ballini, R.; Petrini, M.; Marotta, E.; Righi, P. Org.
Prep. Proc. Int. 1990, 22, 707-746.
13) Barrett, A. G. M.; Graboski, G. G. Chem. Rev. 1986, 86, 751-
62.
(
7
2
2
(
14) Kabalka, G. W.; Varma, R. S. Org. Prep. Proc. Int. 1987, 19,
83-328.
(
160-2162.
(21) (a) Amato, J . Science 1993, 259, 1538-1541. (b) Illman, D. L.
Chem. Eng. News 1993, 71, 5-6. (c) Illman, D. L. Chem. Eng. News
1994, 72, 22-27.
15) Ballini, R.; Castagnani, R.; Petrini, M. J . Org. Chem. 1992, 57,
(
(
16) Ballini, R.; Palestini, C. Tetrahedron Lett. 1994, 35, 5731-5734.
17) Perekalin, V. V. Unsaturated Nitro Compounds; Israel Program
(22) Li, C. J . Chem. Rev. 1993, 93, 2023-2035.
(23) Fringuelli, F.; Pani, G.; Piermatti, O.; Pizzo, F. Tetrahedron
1994, 50, 11499-11508.
for Scientific Translation, J erusalem, 1964.
18) (a) Seebach, D.; Beck, A. K.; Mukhopadhyay, T.; Thomas, E.
(
(24) (a) Rosini, G.; Ballini, R.; Sorrenti, P. Tetrahedron 1983, 39,
4127-4132. (b) Rosini, G.; Ballini, R.; Petrini, M.; Sorrenti, P.
Tetrahedron 1984, 40, 3809-3814. (c) Rosini, G.; Ballini, R.; Petrini,
M. Synthesis 1985, 269-271. (d) Rosini, G.; Ballini, R.; Petrini, M.
Synthesis 1986, 46-48. (e) Ballini, R.; Petrini, M.; Rosini, G. Synthesis
1986, 849-852. (f) Ballini, R.; Petrini, M.; Rosini, G. J . Org. Chem.
1990, 55, 5159-5161. (g) Ballini, R. J . Chem. Soc., Perkin Trans. 1
1991, 1419-1421. (h) Ballini, R.; Bosica, G. J . Chem. Res., Synop. 1993,
371. (i) Ballini, R.; Bosica, G. J . Org. Chem. 1994, 59, 5466-5467.
(25) (a) Ballini, R.; Petrini, M. J . Chem. Soc., Perkin Trans. 1 1992,
3159-3160. (b) Ballini, R.; Bartoli, G. Synthesis 1993, 965-967. (c)
Ballini, R.; Bosica, G. J . Chem. Res. Synop. 1993, 435. (d) Ballini, R.;
Bosica, G. Synthesis 1994, 723-726. (e) Ballini, R.; Bosica, G.;
Schaafstra, R. Liebigs Ann. Chem. 1994, 1235-1237. (f) Ballini, R.;
Bosica, G.; Rafaiani, G. Helv. Chim. Acta 1995, 78, 879-882.
Helv. Chim. Acta 1982, 65, 1101-1133. (b) Eyer, M.; Seebach, D. J .
Am. Chem. Soc. 1985, 107, 3601-3606. (c) Barrett, A. G. W.; Robyr,
C.; Spilling, C. D. J . Org. Chem. 1989, 54, 1233-1234. (d) Sasai, H.;
Suzuki, T.; Arai, S.; Arai, T.; Shibasaki, M. J . Am. Chem. Soc. 1992,
1
14, 4418-4420. (e) Sasai, H.; Itoh, N.; Suzuki, T.; Shibasaki, M.
Tetrahedron Lett. 1993, 34, 855-858. (f) Sasai, H.; Kim, W.-S.; Suzuki,
T.; Shibasaki, M. Tetrahedron Lett. 1994, 35, 6123-6126. (g) Chin-
chilla, R.; N a` jera, C.; Sanchez-Agull o` , P. Tetrahedron: Asymmetry
1
994, 5, 1393-1402.
19) Baer, H. H.; Urbas, L. In The Chemistry of the Nitro and Nitroso
Groups ; Feuer, H., Ed.; Wiley Interscience: New York; 1970; Vol. 2.
20) (a) Rosini, G.; Ballini, R.; Petrini, M.; Sorrenti, P. Synthesis
985, 515-517. (b) Bandgar, B. P.; Zirange, M. B.; Wadgaonkar, P. P.
Synlett 1996, 149-150.
(
(
1
S0022-3263(96)01201-7 CCC: $14.00 © 1997 American Chemical Society

4
26 J . Org. Chem., Vol. 62, No. 2, 1997
Ta ble 1. P r ep a r a tion of â-Nitr oa lk a n ols
Notes
under unexpensive and ecological conditions, with evi-
dent environmental advantages for widespread industrial
use.
Exp er im en ta l Section
Gen er a l P r oced u r es. All 1H NMR spectra were recorded
in CDCl at 300 MHz. Chemical shifts are expressed in ppm
3
downfield from TMS as internal standard. J values are given
in hertz. All the reactions were monitored by TLC. The
2
6
products 3 were purified by flash chromatography on Merck
silica gel (0.040-0.063 mm). Cetyltrimethylammonium chloride
(CTACl) was purchased from Aldrich.
Gen er a l P r oced u r e for th e Nitr oa ld ol (Hen r y) Rea ction .
To a mixture of nitroalkane 1 (50 mmol) and aldehyde 2 (50
mmol), in NaOH 0.025 M (150 mL), was added CTACl (5 mmol)
at room temperature. The mixture was stirred at room tem-
perature for the appropriate time (see Table 1) and then
saturated with NaCl and extracted with Et
organic phase was dried (MgSO ) and concentrated, and the
2
O (4 × 30 mL). The
4
crude nitro alcohol 3, if necessary, was purified by flash
chromatography (EtOAc/cyclohexane, 2:8).
1
-P h en yl-2-n itr oeth a n -1-ol (en tr y 3a ): IR ν ) 3400, 1535
-1 1
cm ; H NMR (CDCl
3
) δ ) 2.6 (m, 1H), 4.47-4.68 (m, 2H), 5.41-
.54 (m, 1H), 7.2-7.58 (m, 5H). Anal. Calcd for C NO C,
7.48; H, 5.42; N, 8.37. Found: C, 57.65; H, 5.29; N, 8.44.
5
5
8
H
9
3
8
1
-P h en yl-2-n itr obu ta n -1-ol (en tr y 3b): IR ν ) 3400, 1530
-
1 1
cm ; H NMR (CDCl
3
) δ ) 0.87 (t, 2.4 H, J ) 7.4 Hz), 0.94 (t,
.6 H, J ) 7.4 Hz), 1.3-2.0 (m, 2H), 4.5-4.7 (m, 1H), 5.03 (d,
.8 H, J ) 9.2 Hz), 5.2 (d, 0.2 H, J ) 4.8 Hz), 7.25 -7.45 (m,
H). Anal. Calcd for C10 C, 61.52; H, 6.71; N, 7.17.
0
0
5
H
13NO
3
Found: C, 61.21; H, 6.99; N, 6.98.
8
,9
1
-(2-F u r a n yl)-2-n itr op r op a n -1-ol (en tr y 3c):
IR ν )
) δ ) 1.4 (d, 2H, J ) 6.6 Hz),
.6 (d, 1H, J ) 6.9 Hz), 2.5 (m, 1H), 4.8-5.1 (m, 2H), 6.35-6.42
NO C, 49.12;
H, 5.30; N, 8.18. Found: C, 48.95; H, 5.18; N, 8.30.
-(p-Nitr op h en yl)-2-n itr op r op a n -1-ol (en tr y 3d ): IR ν )
3
1
8
-
1 1
3
1
(
420, 1540 cm ; H NMR (CDCl
3
m, 2H), 7.4-7.45 (m, 1H). Anal. Calcd for C
7
H
9
4
1
-
1 1
3
400, 1600, 1530 cm ; H NMR (CDCl ) δ ) 1.45 (dd, 3H, J )
9.6, 6.9 Hz), 2.8 (m, 1H), 4.65-4.85 (m, 1H), 5.2 (d, 0.6 H, J )
.1 Hz), 5.55 (d, 0.4 H, J ) 4.7 Hz), 7.6 (d, 2H, J ) 5 Hz), 8.25
(
d, 2 H, J ) 5 Hz). Anal. Calcd for C
9 10 2 5
H N O C, 47.79; H, 4.45;
N, 12.38. Found: C, 48.01; H, 4.26; N, 12.52.
1
-(p-Nitr op h en yl)-2-n itr oh exa n -1-ol (en tr y 3e): IR ν )
1 1
-
3
3
480, 1600, 1530, 1510 cm ; H NMR (CDCl
H), 1.1-2.0 (m, 6H), 4.6-4.75 (m, 1H), 5.15 (d, 0.7 H, J ) 8.1
3
) δ ) 0.8-1.0 (m,
Hz), 5.35 (d, 0.3 H, J ) 4.0 Hz), 7.58 (d, 0.7 H, J ) 8.9 Hz), 8.05
d, 0.3 H, J ) 9.0 Hz), 8.26 (d, 0.7 H, J ) 8.9 Hz), 8.4 (d, 0.3 H,
C, 53.72; H, 6.01; N,
(
J ) 9.0 Hz). Anal. Calcd for C12
16 2 5
H N O
1
0.44. Found: C, 53.88; H, 5.8; N, 10.58.
1
-P h en yl-4-n itr oh ep ta n -3-ol (en tr y 3f): IR ν ) 3400, 1600,
aromatic ones. Short times (2-6 h) are required, and
both primary and secondary nitroalkanes give good
results.
-1 1
1
2
540 cm ; H NMR (CDCl
3
) δ ) 0.8-1.0 (m, 3 H), 1.2-1.45 (m,
H), 1.6-2.2 (m, 4 H), 2.6-3.0 (m, 2 H), 3.8-3.92 (m, 0.7 H),
4.0-4.1 (m, 0.3 H), 4.4-4.6 (m, 1 H). Anal. Calcd for C13
H19NO
3
Contrary to other methods, the success of this approach
C, 65.80; H, 8.07; N, 5.90. Found: C, 66.01; H, 8.23; N, 6.08.
1
d,4,15
4
,8
2-Nitr o-5-p h en ylp en ta n -3-ol (en tr y 3g):
IR ν ) 3400,
) δ ) 0.85 (t, 3 H, J ) 7.2 Hz),
.05-1.6 (m, 8 H), 1.7-2.2 (m, 4 H), 3.8-4.05 (m, 1 H), 4.3-
is independent from the ratio catalyst/substrates and
-
1 1
1
d,9
1600, 1550 cm ; H NMR (CDCl
3
does not need long reaction times,
tedious preparation
1
4
of the catalyst,4 large excess of the nitroalkane,4 or
severe reaction conditions that are too cumbersome,
especially for large-scale preparations.3 Additionally, the
very mild reaction conditions prevent the typical side
,9
.42 (m, 1 H), 7.15-7.38 (m, 5 H). Anal. Calcd for C11H15NO
3
C, 63.14; H, 7.22; N, 6.69. Found: C, 63.00; H, 6.98; N, 6.90.
1-(Te t r a h yd r op yr a n yloxy)-2-n it r o-5-p h e n ylp e n t a n -
-
1 1
3-ol (en tr y 3h ): IR ν ) 3350, 1540 cm ; H NMR (CDCl
1.1-2.0 (m, 8 H), 2.5-3.05 (m, 2 H), 3.3-4.4 (m, 5 H), 4.5-4.8
(m, 1 H), 7.12-7.35 (m, 5 H). Anal. Calcd for C16 C,
2.12; H, 7.49; N, 4.52. Found: C, 61.87; H, 7.29; N, 4.35.
-(3-Nitr o-4-h yd r oxy-6-p h en ylh exyl)-1,3-d ioxola n e (en -
3
) δ )
1
reactions such as retro-aldol reaction or dehydration of
2
0
H23NO
5
the 2-nitro alcohols into nitroalkenes even if aromatic
aldehydes are used. High chemoselectivity is observed
since several functionalities such as hydroxy group, ester,
acetal, tetrahydropyranyl, (Z)-C,C double bond, and furyl
are preserved under these conditions. Moreover, if a
nitro ketone is employed as a functionalized nitro deriva-
tive (entry 3q ), multiple nitroaldol reactions were not
observed.
6
2
-1
1
tr y 3i): IR ν ) 3410, 1535 cm ; H NMR (CDCl ) δ ) 1.5-2.2
(m, 6 H), 2.6-2.97 (m, 2 H), 3.75-4.0 (m, 5 H), 4.0-4.2 (m, 1
H), 4.45-4.61 (m, 1 H), 4.88 (t, 1 H, t, J ) 4.2 Hz), 7.12-7.35
3
(
m, 5 H). Anal. Calcd for C15
Found: C, 61.31; H, 7.41; N, 4.54.
-Meth yl-2-n itr o-5-p h en ylp en ta n -3-ol (en tr y 3j): IR ν )
5
H21NO C, 61.00; H, 7.16; N, 4.74.
1
d
2
-
1 1
3
(
450, 1550 cm ; H NMR (CDCl
m + s, 5 H), 2.6 (m, 1 H), 2.65-3.05 (m, 2 H), 4.02 (dd, 1 H, J
3
) δ ) 1.62 (s, 3 H), 1.6-1.85
Compared with the conventional methods,1-9,17,19our
procedure produces better yields in shorter reaction times
even with complex starting materials and, at last, allows
us to perform this important reaction on a gram scale
(
26) Still, W. C.; Kahan, M.; Mitra, A. J . Org. Chem. 1978, 43, 2923-
2926.

Notes
J . Org. Chem., Vol. 62, No. 2, 1997 427
)
1.9, 10.2 Hz), 7.15-7.4 (m, 5 H). Anal. Calcd for C12
H
17NO
3
3.95 (m, 0.6 H), 3.96-4.08 (m, 0.4), 4.4-4.55 (m, 1 H), 5.3-5.42
C, 64.55; H, 7.67; N, 6.27. Found: C, 64.35; H, 7.95; N, 6.44.
3
(m, 2 H). Anal. Calcd for C22H43NO C, 71.49; H, 11.72; N, 3.79.
1
d,9
Found: C, 71.65; H, 11.99; N, 3.62.
5-Nitr o-6-h yd r oxy-7-m eth yld eca n -2-on e (en tr y q): IR ν
1
-Cycloh exyl-2-n itr op r op a n -1-ol (en tr y 3k ):
IR ν )
) δ ) 0.9-2.1 (m, 11 H), 1.55
dd, 3 H, J ) 3.7, 6.9 Hz), 3.6-3.7 (m, 0.5 H), 3.92-4.0 (m, 0.5
H), 4.58-4.78 (m, 1 H). Anal. Calcd for C C, 57.73; H,
-
1 1
3
420, 1540 cm ; H NMR (CDCl
3
-
1 1
)
3460, 1700, 1540 cm ; H NMR (CDCl
H), 0.95 (d, 3 H, J ) 7.2 Hz), 1.17-1.58 (m, 5 H), 1.78-2.25 (m,
H), 2.16 (s, 3 H), 2.48-2.58 (m, 3 H), 3.65 (t, 0.2 H, J ) 6.2
Hz), 3.89 (dd, 0.8 H, J ) 3.5, 8.3 Hz), 4.57-4.78 (m, 1 H). Anal.
Calcd for C11 C, 57.12; H, 9.15; N, 6.05. Found: C, 57.35;
H, 9.29; N, 6.23.
Meth yl 4-n itr o-5-h yd r oxyh ep ta n oa te (en tr y 3r ): IR ν
3
) δ ) 0.86-1.03 (m, 3
(
9
H17NO
3
2
9
.15; N, 7.48. Found: C, 57.65; H, 9.34; N, 7.23.
1
5
1
-Cycloh exyl-2-n itr oh ep ta n -1-ol (en tr y 3l): IR ν ) 3500,
1 1
-
H21NO
4
1
545 cm ; H NMR (CDCl ) δ ) 0.85 (m, 3 H), 1.0-2.15 (m, 19
3
H), 3.55-3.65 (m, 0.5 H), 3.7-3.8 (m, 0.5 H), 4.5-4.7 (m, 1 H).
Anal. Calcd for C13 C, 64.16; H, 10.35; N, 5.75. Found:
C, 64.42; H, 10.08; N, 5.38.
-Nitr o-5-(5-m eth yl-2-fu r a n yl)p en ta n -3-ol (en tr y 3m ): IR
1
d
H
25NO
3
-
1 1
)
3425, 1715, 1510 cm ; H NMR (CDCl
J ) 7.3 Hz), 1.45-1.7 (m, 2 H), 2.1-2.6 (m, 4 H), 3.68 (s, 3 H),
.8-3.9 (m, 0.6 H), 3.95-4.05 (m, 0.4 H), 4.48-4.65 (m, 1 H).
Anal. Calcd for C C, 46.82; H, 7.36; N, 6.82. Found:
C, 47.04; H, 7.29; N, 6.59.
Meth yl 8-n itr o-9-h yd r oxyu n d eca n oa te (en tr y 3s): IR ν
3
) δ ) 1.0-1.1 (t, 3 H,
2
3
-
1 1
ν ) 3320, 1530 cm ; H NMR (CDCl
3
) δ ) 1.58 (dd, 3 H, J )
.9, 10 Hz), 1.62-2.0 (m, 2 H), 2.27 (s, 3 H), 2.65-2.95 (m, 2 H),
.87-4.00 (m, 0.6 H), 4.2-4.3 (m, 0.4 H), 4.45-4.62 (m, 1 H),
.82-5.92 (m, 2 H). Anal. Calcd for C10 C, 56.32 H, 7.09;
8
H15NO
5
3
3
5
H
15NO
4
-
1 1
)
)
(
3450, 1715, 1535 cm ; H NMR (CDCl
3
) δ ) 1.12 (dt, 3 H, J
N, 6.56. Found: C, 56.11; H, 7.29; N, 6.44.
1.9, 7.3 Hz), 1.2-2.1 (m, 12 H), 2.3 (t, 2 H, J ) 7.3 Hz), 3.62
(
Z)-8-Nitr otr id ec-3-en -7-ol (en tr y 3n ): IR ν ) 3300, 1560
s, 3 H), 3.7-3.87 (m, 0.6 H), 3.87-4.0 (m, 0.4 H), 4.38-4.52
-
1 1
cm ; H NMR (CDCl
.2-1.4 (m, 6 H), 1.5-1.6 (m, 2 H), 1.65-1.85 (m, 2 H), 1.95-2.3
m, 4 H), 3.85-3.95 (m, 0.6 H), 4.0-4.1 (m, 0.4 H), 4.35-4.5 (m,
3
) δ ) 0.8-0.9 (m, 3 H), 0.9-1.0 (m, 3 H),
(
m, 1 H). Anal. Calcd for C12 C, 55.15; H, 8.87; N, 5.35.
H
23NO
5
1
(
Found: C, 55.33; H, 9.03; N, 5.50.
-(1-Nitr ocycloh exyl)p r op a n -1-ol (en tr y 3t): IR ν ) 3450,
1
1
1
H), 5.2-5.5 (m, 2 H). Anal. Calcd for C13
0.35; N, 5.75. Found: C, 63.93; H, 10.24; N, 5.57.
Z)-8-Nitr otetr a d ec-3-en e-7,14-d iol (en tr y 3o): IR ν )
H
25NO
3
C, 64.16; H,
-1 1
1
520 cm ; H NMR (CDCl
H, J ) 8.5 Hz), 2.4-2.6 (m, 2 H), 3.5 (dd, 1 H, J ) 1.8, 10.1 Hz).
Anal. Calcd for C C, 60.28; H, 8.59; N, 7.03. Found:
C, 60.06; H, 8.40; N, 6.88.
3
) δ ) 0.85-1.78 (m, 10 H), 1.25 (t, 3
(
9
H17NO
3
-
1 1
3
1
350, 1540 cm ; H NMR (CDCl
3
) δ ) 0.95 (t, 3 H, J ) 7.4 Hz),
.2-2.3 (m, 16 H), 3.65 (t, 2 H, J ) 6.4 Hz), 3.8-3.95 (m, 0.5
H), 3.96-4.1 (m, 0.5 H), 4.32-4.52 (m, 1 H), 5.2-5.5 (m, 2 H).
Anal. Calcd for C14 C, 61.51; H, 9.95; N, 5.12. Found:
C, 61.24; H, 10.19; N, 5.34.
Z)-19-Nitr otr od ocos-9-en -18-ol (en tr y 3p ): IR ν ) 3450,
Ack n ow led gm en t. We are grateful to Professor F.
Fringuelli (Perugia University) for useful discussions.
This work was supported by C.N.R.-Italy and the
University of Camerino-Italy.
H
27NO
4
(
-
1 1
1
535 cm ; H NMR (CDCl
3
) δ ) 0.88 (t, 3 H, J ) 7.1 Hz), 0.95
(t, 3 H, J ) 7.2 Hz), 1.1-1.6 (m, 28 H), 1.9-2.15 (m, 4 H), 3.78-
J O961201H