Cetyltrimethylammonium hydroxide (CTAOH) as a general, ecofriendly catalyst for the formation of carbon-carbon bond through nitroalkanes

Article abstract of DOI:10.1016/j.tet.2004.01.067

Nitroalkanes have been found to give good yields in Michael and nitroaldol (Henry) reactions by the use of a catalytic amount (10mol%) of CTAOH, at room temperature and under solvent free conditions and in very short reaction times. The methods do not nee

Full text of DOI:10.1016/j.tet.2004.01.067

Tetrahedron 60 (2004) 2799–2804
Cetyltrimethylammonium hydroxide (CTAOH) as a general,
ecofriendly catalyst for the formation of carbon–carbon bond
through nitroalkanes
*
Roberto Ballini, Dennis Fiorini, Maria Victoria Gil and Alessandro Palmieri
`
Dipartimento di Scienze Chimiche, Universita di Camerino, Via S. Agostino 1, 62032 Camerino, Italy
Received 21 October 2003; revised 23 December 2003; accepted 22 January 2004
Abstract—Nitroalkanes have been found to give good yields in Michael and nitroaldol (Henry) reactions by the use of a catalytic amount
(10 mol%) of CTAOH, at room temperature and under solvent free conditions and in very short reaction times. The methods do not need a
large excess of the nitroalkanes and show good chemoselectivity toward further functionalities.
q 2004 Elsevier Ltd. All rights reserved.
1. Introduction
ment of new technologies for environmentally benign
processes (green chemistry). An important area of the
green chemistry deals with solvent minimization,11–13 and
new efficient, economical and environmentally friendly
catalytic processes for both Henry and Michael reactions,
are desirable.
Carbon–carbon bond formation is the essence of organic
synthesis and nitroalkanes are very important starting
materials in this context.1,3 This is mainly due to their
easy conversion into the corresponding nitronate anions
because the high electron-withdrawing power of the nitro
group that provides an outstanding enhancement of the
acidity of a-hydrogens atoms. Therefore, nitronate salts can
act as carbon nucleophiles with a range of electrophiles such
as aldehydes, giving the nitroaldol (Henry reaction),4,5 or
with electron poor alkenes, giving the conjugate addition
(Michael) reaction.6 As routine procedures the Henry and
Michael reactions are performed in the presence of different
bases in homogeneous solutions of organic solvent or water
or, alternatively, under heterogeneous catalysis6,7 and, for
these purposes, even the help of sonication8 or high
pressure9,10 have been proposed. Although each of the
above procedures have been widely studied, very often
these suffer from different drawbacks such as: (i) for the
nitroaldol reaction, low yields, retroaldol reaction, the
formation of side products due to the aldol condensation
and/or Cannizzaro reaction of aldehydes or olefin formation,
and (ii), for the Michael reaction, low yields, efficiency
restricted to a class of electrophilic olefins, the need of
ultrasound, and/or a large excess of the nitroalkane that, for
valuable nitro derivatives, is a serious economic drawback.
2. Results and discussion
In this context, we report herein a new catalytic approach
developed in our laboratory, and carried out with cetyl-
trimethylammonium hydroxide (CTAOH, 10% water
solution) as ecofriendly catalyst. First, we investigated the
Michael reaction and, in order to verify the best sub-
strates/catalyst ratio, the method was tested (Scheme 1)
through the reaction of 1-nitropentane 1d with an hindered
electrophilic alkene such as 2-cyclohexen-1-one 2b.
Scheme 1.
Thus, considering that over the past few years, a significant
amount of research has been directed towards the develop-
The choice of this model reaction is due to the well known
behaviour of the conjugate additions of nitroalkanes to 2b
that, generally, need long reaction times and the Michael
adducts are generally obtained in low to satisfactory yields,
probably due to the steric hindrance of the acceptor.2,6 The
reaction was performed by adding the Michael acceptor 2b
Keywords: Henry reaction; Michael reaction; Nitroalkanes; b-Nitroalcohol;
CTAOH.
*
Corresponding author. Tel.: þ39-0737-402270; fax: þ39-0737-402297;
e-mail address: roberto.ballini@unicam.it
0040–4020/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2004.01.067

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R. Ballini et al. / Tetrahedron 60 (2004) 2799–2804
Table 1. Study of Michael addition of 1-nitropentane 1d to 2-cyclohexen-2-
one 2b with different amount of CTAOH (reaction time 2 h)
% of CTAOH
Yield (%) of 3db
2.5
5
10
15
20
30
65
90
91
90
Scheme 3.
conditions to the nitroaldol reaction investigating the
reactivity of a series of linear and cyclic nitroalkanes 1
with an array of both aliphatic and aromatic aldehydes 4
(Scheme 3).
Although these reactions are slower than the conjugate
additions (2–6 h vs 1–2 h), we found that the b-nitro-
alcohols 5 are produced in good yields (68–86%, Table 3)
and contrary to other methods, the very mild reaction
conditions needed prevent the typical side reactions such as
retro-aldol reaction or dehydration of the 2-nitro alcohol
into nitroalkenes, even if aromatic aldehydes are used.14,15
3. Conclusion
In summary, we have reported general catalytic method for
the formation of carbon–carbon bond using nitroalkanes
with several electrophilic alkenes (such as a,b-unsaturated
ketones, a,b-unsaturated esters, a,b-unsaturated suphones,
and a,b-unsaturated nitriles) and both aromatic and
aliphatic aldehydes. All the reactions work well with short
reaction times, mild reaction conditions (room temperature
and 10% of the catalyst), in the presence of a minimum
amount of water. High chemoselectivity is observed since
further functionalities are preserved under these conditions.
It is noteworthy that our method avoids the need for a large
excess of the nitroalkanes and uses organic solvents during
the work up only. Thus, because an important area of green
chemistry deals with solvents16,17 and by products mini-
mization our results represent an improved, inexpensive and
ecological process.
Figure 1. Trend of Michael adduct 3db with different amount of CTAOH.
to an equimolar amount of a stirred mixture of 1d and in the
presence of different quantities of CTAOH (Table 1, Fig. 1).
As reported in Figure 1, 10 mol% of the catalyst was found
to be most appropriate and the Michael adduct 3db was
obtained in excellent yield (90%) and in a very short
reaction time (2 h, Table 1).
Thus, a number of different nitroalkanes 1 and electron poor
alkenes 2 were chosen to assess the scope of the reaction
(Scheme 2).
4. Experimental
4.1. General
1H NMR were recorded at 300 MHz on a Varian VXR300 in
CDCl3 as solvent. 13C NMR were recorded at 75 MHz in
CDCl3 as solvent. Microanalyses were performed with a
CHNS-O analyser MODEL EA 1108 from Fisons Instru-
ments. IR spectra were recorded with a Perkin–Elmer
Paragon 500 FT-IR. GLC analyses were performed on a
fised silica (0.32 mm£25 m), stationary phase SE54. Mass
spectra were performed on a Hewlett–Packard GC/MS
5970 by means of the EI technique (70 eV). CTAOH was
supplied by Fluka as a 10% water solution.
Scheme 2.
All the reactions were carried out in the presence of a
minimum amount of water (due to the use of 10% water
solution of the catalyst) and involved simple mixing
stoichiometric amounts of 1 (1 mmol) and 2 (mmol) with
10% mol% of CTAOH (10% water solution), at room
temperature, and leaving the mixture for further 1–2 h.
The synthetic results of the reactions are presented in
Table 2. Under this method simple and functionalized
nitroalkanes easily react with a variety of electrophilic
alkenes, and the yields seem to be fairly independent of the
degree of electron-deficiency of the alkene and of steric
hindrance (3bb,db). It is worthy of note that this procedure
affords compounds 3 in good yields (65–90%). Encouraged
by these excellent results, we applied the same reaction
4.2. General procedure for the Michael reaction
The Michael acceptor 2 (1 mmol) was added to a stirred
mixture of nitrocompound 1 (1 mmol; when the nitro-
alkanes 1a and 1b were employed 1.2 mmol were utilised)
in a 10% water solution of hexadecyltrimethyl ammonium

R. Ballini et al. / Tetrahedron 60 (2004) 2799–2804
Table 2. Michael addition of nitro compounds 1 to a,b-unsaturated systems 2
2801
Nitro compound 1
a,b-Unsaturated
compound 2
Michael adduct 3
Time (h)
Yield (%)a
1a
2a
2b
3aa
3bb
1
78
80
1b
1
1b
1c
1c
1d
2c
2a
2c
2d
3bc
3ca
3cc
3dd
1
1
1
1
83
77
75
74
1d
2b
3db
2
90
1e
1e
1e
2a
2e
2f
3ea
3ee
3ef
1
1
1
87
70
70
1e
1f
2d
2f
3ed
3ff
1
2
2
1
77
73
65
72
1g
1h
2e
2e
3ge
3he
a
Yields of pure, isolated compounds.

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R. Ballini et al. / Tetrahedron 60 (2004) 2799–2804
Table 3. Addition of nitro compounds 1 to aldehydes 4
Nitro compound 1
Aldehyde 4
Nitroalcohol 5
Time (h)
Yield (%)a
1b
4a
4b
4c
4b
4d
5ba
5cb
5dc
5eb
5ed
3
82
1c
1d
1e
1e
2
3
3
4
83
85
81
75
1e
1e
4e
4f
5ee
5ef
4
6
76
68
1f
1i
4b
4g
4i
5fb
5ig
5ji
3
4
3
4
77
83
86
75
1j
1k
4h
5kh
a
Yields of pure, isolated compounds.
hydroxide (CTAOH, 0.300 mL). The reaction progress was
monitored by withdrawing aliquots which were analyzed by
GC and TLC. Then the solution was treated with brine
(10 mL) and extracted by CH2Cl2 (3£25 mL). The organic
layer was dried over anhydrous Na2SO4, filtered, concen-
trated under vacuum to afford the crude product 3, that was
purified on flash cromatography (cyclohexane–ethyl acetate).
Spectroscopic data corresponds to that reported in the
literature.19
4.2.3. 6-Nitro-3-octanone (3bc). Yield 83% of colourless
oil. Spectroscopic data corresponds to that reported in the
literature.20
4.2.4. Methyl-4-nitroheptanoate (3ca). Yield 77% of
1
4.2.1. Methyl-4-nitropentanoate (3aa). Yield 78% of
yellow oil. Spectroscopic data corresponds to that reported
in the literature.18
yellow oil; IR (cm21, neat) 1364, 1560, 1740; H NMR d
(ppm) 0.95 (t, 3H, J¼7.3 Hz), 1.28–1.47 (m, 2H), 1.61–
1.81 (m, 1H), 1.90–2.42 (m, 5H), 3.70 (s, 3H), 4.52–4.65
(m, 1H); 13C NMR d (ppm) 13.5, 19.1, 28.7, 30.0, 35.9,
52.0, 87.6, 172.5; EI-MS: m/z¼190, 172, 158, 143, 127,
111, 83, 69, 55 (100), 41. Anal. calcd for C8H15NO4
4.2.2. 3-(1-Nitropropyl)-1-cyclohexanone (3bb). (Dia-
stereomeric mixture, 1:1). Yield 80% of yellow oil.

R. Ballini et al. / Tetrahedron 60 (2004) 2799–2804
2803
(189.21) C, 50.78; H, 7.99; N, 7.40. Found: C, 50.93; H,
8.12; N, 7.29.
122, 96, 82, 67, 55, 45 (100), 39. Anal. calcd for C8H14N2O3
(186.21) C, 51.60; H, 7.58; N, 15.04. Found: C, 51.77; H,
7.66; N, 14.95.
4.2.5. 6-Nitro-3-nonanone (3cc). Yield 75% of colourless
1
oil; IR (cm21, neat) 1363, 1548, 1717; H NMR d (ppm)
4.3. General procedure for the Henry reaction
0.95 (t, 3H, J¼7.3 Hz), 1.07 (t, 3H, J¼6.4 Hz), 1.22–1.43
(m, 2H), 1.60–1.79 (m, 1H), 1.89–2.18 (m, 3H), 2.38–2.52
(m, 4H), 4.42–4.60 (m, 1H); 13C NMR d (ppm) 7.7, 13.1,
18.9, 29.4, 34.5, 36.0, 40.1, 83.0, 208.5; EI-MS: m/z¼188,
157, 141, 127, 110, 83, 69, 57 (100), 41. Anal. calcd for
C9H17NO3 (187.24) C, 57.73; H, 9.15; N, 7.48. Found: C,
57.88; H, 9.06; N, 7.39.
The aldehyde 4 (1 mmol) was added to a stirred mixture of
nitrocompound 1 (1 mmol) in a 10% water solution of
hexadecyltrimethyl ammonium hydroxide (0.300 mL). The
reaction progress was monitored by withdrawing aliquots
which were analyzed by TLC. Then the solution was treated
with brine (10 mL) and extracted by CH2Cl2 (3£25 mL).
The organic layer was dried over anhydrous Na2SO4,
filtered, concentrated under vacuum to afford the crude
product 5, that was purified on flash cromatography
(cyclohexane–ethyl acetate).
4.2.6. 5-Nitro-2-nonanone (3dd). Yield 74% of colourless
oil. Spectroscopic data corresponds to that reported in the
literature.20
4.2.7. 3-(1-Nitropentyl)-1-cyclohexanone (3db). (Dia-
stereomeric mixture, 1:1). Yield 90% of yellow oil. Spectro-
scopic data corresponds to that reported in the literature.20
4.3.1. 3-Nitro-4-tridecanol (5ba). Yield 82% of yellow oil;
IR (cm21, neat) 1377, 1559, 3435; 1H NMR d (ppm) 0.83–
0.90 (m, 3H), 0.93–1.02 (m, 3H), 1.18–1.56 (m, 16H),
1.78–2.19 (m, 2H), 2.46–2.52 (m, 0.5H), 2.58–2.62
(m, 0.5H), 3.82–3.92 (m, 0.5H), 3.94–4.02 (m, 0.5H),
4.30–4.41 (m, 1H); 13C NMR d (ppm) 10.4, 10.7, 14.3,
21.8, 22.9, 24.1, 25.5, 25.8, 29.4, 29.5, 29.6, 29.7, 29.8,
32.1, 33.5, 33.7, 72.0, 72.4, 94.2, 94.7. Anal. calcd for
C13H27NO3 (245.36) C, 63.64; H, 11.09; N, 5.71. Found: C,
63.75; H, 11.20; N, 5.58.
4.2.8. Methyl-4-nitrononanoate (3ea). Yield 87% of
yellow oil. Spectroscopic data corresponds to that reported
in the literature.18
4.2.9. 4-Nitrononanenitrile (3ee). Yield 70% of yellow oil.
Spectroscopic data corresponds to that reported in the
literature.21
4.3.2. 4-Nitro-5-decanol (5cb). Yield 83% of colourless oil;
IR (cm21, neat) 1380, 1560, 3436; 1H NMR d (ppm) 0.82–
1.01 (m, 6H), 1.22–1.57 (m, 10H), 1.62–1.85 (m, 1H),
1.95–2.15 (m, 1H), 2.20–2.38 (m, 0.5H), 2.35–2.40 (m,
0.5H), 3.80–3.90 (m, 0.5H), 3.93–4.05 (m, 0.5H), 4.41–
4.55 (m, 1H); 13C NMR d (ppm) 13.6, 13.7, 14.2, 19.3, 19.5,
22.7, 25.2, 25.5, 30.1, 31.7, 31.8, 32.7, 33.4, 33.8, 72.3,
72.6, 92.3, 92.9. Anal. calcd for C10H21NO3 (203.28) C,
59.09; H, 10.41; N, 6.89. Found: C, 59.23; H, 10.55; N, 6.77.
4.2.10. 3-Nitro-1-(phenylsulfonyl)octane (3ef). Yield 70%
of yellow oil. Spectroscopic data corresponds to that
reported in the literature.21
4.2.11. 5-Nitro-2-decanone (3ed). Yield 77% of colourless
oil. Spectroscopic data corresponds to that reported in the
literature.22
4.2.12. Methyl-6-nitro-8-(phenylsulfonyl)octanoate (3ff).
Yield 73% of yellow oil; IR (cm21, neat) 1308, 1556, 1732;
1H NMR d (ppm) 1.22–1.41 (m, 2H), 1.58–1.82 (m, 3H),
1.90–2.09 (m, 1H), 2.21–2.39 (m, 4H), 3.11 (t, 2H,
J¼7.4 Hz), 3.67 (s, 3H), 4.58–4.67 (m, 1H), 7.58–7.93
(m, 5H); 13C NMR d (ppm) 24.2, 25.2, 26.6, 33.5, 33.6,
51.8, 52.5, 86.5, 128.2, 129.8, 134.4, 138.8, 173.7; EI-MS:
m/z¼265, 171, 143, 123, 95, 77 (100), 67, 55, 41. Anal.
calcd for C15H21NO6S (343.39) C, 52.47; H, 6.16; N, 4.08.
Found: C, 52.59; H, 6.30; N, 3.99.
4.3.3. 1-Bicyclo[2.2.1]hept-5-en-2-yl-nitrohexan-1-ol
(5dc). Yield 85% of white solid, mp 43–45 8C; IR (cm21
,
1
neat) 1365, 1543, 1625, 3040, 3420; H NMR d (ppm)
0.83–1.05 (m, 3H), 1.22–1.57 (m, 7H), 1.70–2.38 (m, 5H),
2.82–2.94 (m, 1H), 3.02–3.12 (m, 1H), 4.38–4.76 (m, 2H),
5.82–6.27 (m, 2H); 13C NMR d (ppm) 13.9, 22.3, 28.0,
28.1, 28.4, 29.6, 29.8, 30.7, 42.6, 44.4, 49.1, 49.2, 50.1,
50.2, 75.8, 76.0, 91.3, 91.4, 132.5, 132.6, 138.3, 138.5.
Anal. calcd for C13H21NO3 (239.31) C, 65.25; H, 8.84; N,
5.85. Found: C, 65.39; H, 8.99; N, 5.77.
4.2.13. 4-Nitro-7-oxooctanenitrile (3ge). Yield 65% of
1
yellow oil; IR (cm21, neat) 1363, 1560, 1729, 2249; H
4.3.4. 7-Nitro-6-dodecanol (5eb). Yield 81% of colourless
1
NMR d (ppm) 2.02–2.25 (m, 6H), 2.33–2.60 (m, 5H),
4.57–4.70 (m, 1H); 13C NMR d (ppm) 14.4, 27.2, 29.4,
30.2, 38.8, 85.9, 117.9, 206.2; EI-MS: m/z¼185, 155, 113,
95, 71, 55, 43 (100). Anal. calcd for C8H12N2O3 (184.24) C,
52.17; H, 6.57; N, 15.21. Found: C, 52.31; H, 6.66; N, 15.08.
oil; IR (cm21, neat) 1379, 1561, 3447; H NMR d (ppm)
0.82–1.05 (m, 6H), 1.19–1.90 (m, 15H), 2.01–2.42 (m, 2H)
3.80–3.91 (m, 0.5H), 3.93–4.12 (m, 0.5H), 4.38–4.59 (m,
1H); 13C NMR d (ppm) 13.7, 14.3, 21.9, 23.0, 24.3, 28.4,
28.5, 30.1, 31.0, 31.2, 33.8, 33.9, 72.9, 73.1, 92.9, 93.0.
Anal. calcd for C12H25NO3 (231.33) C, 62.30; H, 10.89; N,
6.05. Found: C, 62.15; H, 11.00; N, 5.98.
4.2.14. 7-Hydroxy-4-nitrooctanenitrile (3he). (Dia-
stereomeric mixture 1:1). Yield 72% of yellow oil; IR
(cm21, neat) 1376, 1552, 2250, 3422; 1H NMR d (ppm) 1.21
(d, 3H, J¼6.2 Hz), 1.41–1.55 (m, 2H), 1.71–1.82 (bs, 1H),
1.95–2.49 (m, 6H), 3.71–3.92 (m, 1H), 4.58–4.76 (m, 1H);
13C NMR d (ppm) 14.5, 24.0, 24.1, 29.2, 29.4, 29.8, 30.3,
34.5, 34.9, 66.8, 67.4, 86.6, 87.2, 118.1; EI-MS: m/z¼171,
4.3.5. 4-Nitro-1-phenyl-3-nonanol (5ed). Yield 75%
yellow oil; IR (cm21, neat) 1376, 1560, 1603, 3027, 3448;
1H NMR d (ppm) 0.83–0.99 (m, 3H), 1.21–1.40 (m, 6H),
1.68–2.17 (m, 4H) 2.38–2.45 (m, 0.5H), 2.51–2.56 (m,
0.5H), 2.62–3.01 (m, 2H), 3.82–4.11 (m, 1H), 4.41–4.57

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R. Ballini et al. / Tetrahedron 60 (2004) 2799–2804
(m, 1H), 7.18–7.37 (m, 5H); 13C NMR d (ppm) 14.0, 14.1,
22.5, 25.5, 25.8, 28.2, 30.6, 31.3, 31.4, 31.8, 32.0, 35.0,
35.5, 71.5, 71.8, 92.6, 93.2, 126.5, 128.7, 128.8, 141.0,
141.1. Anal. calcd for C15H23NO3 (265.35) C, 67.90; H,
8.74; N, 5.28. Found: C, 68.03; H, 8.86; N, 5.19.
75% of yellow oil. Spectroscopic data corresponds to that
reported in the literature.24
Acknowledgements
4.3.6. 2-Nitro-1-(4-nitrophenyl)-1-heptanol (5ee). Yield
76% of yellow oil; IR (cm21, neat) 1349, 1520, 1556, 1607,
3082, 3522; H NMR d (ppm) 0.81–0.97 (m, 3H), 1.09–
This work was supported by the University of Camerino-
Italy and by MIUR-Italy (Project ‘Il Mezzo Acquoso nelle
Applicazioni Sintetiche dei Nitrocomposti Alifatici’).
1
1.40 (m, 6H), 1.62–2.13 (m, 2H), 3.03 (bs, 1H), 4.61–4.77
(m, 1H), 5.05–5.10 (m, 0.5H), 5.13–5.18 (m, 0.5H), 7.60
(d, 2H, J¼8.3 Hz), 8.22 (d, 2H, J¼8.3 Hz); 13C NMR d
(ppm) 13.9, 22.4, 25.4, 25.6, 27.5, 27.7, 30.4, 31.0, 31.1,
73.6, 74.7, 92.9, 93.3, 124.1, 124.3, 128.0, 145.9, 148.5.
Anal. calcd for C13H18N2O5 (282.29) C, 55.31; H, 6.43; N,
9.92. Found: C, 55.44; H, 6.24; N, 9.85.
References and notes
1. (a) Seebach, D.; Colvin, E. W.; Weller, F.; Weller, T. Chimia
1979, 33, 1–18. (b) Bhattacharya, A.; Purohit, V. C.; Rinaldi,
F. Org. Process Res. Dev. 2003, 7, 254–258.
2. Rosini, G.; Ballini, R. Synthesis 1988, 833–847.
3. Rosini, G.; Ballini, R.; Petrini, M.; Marotta, E.; Righi, P. Org.
Prep. Proced. Int. 1990, 22, 707–746.
4.3.7. 2-Nitro-1-phenyl-1-heptanol (5ef). Yield 68% of
yellow oil. Spectroscopic data corresponds to that reported
in the literature.23
4. Rosini, G. In Comprehensive organic synthesis; Trost, B. M.,
Ed.; Pergamon: New York, 1992; pp 321–340.
5. Luzzio, F. A. Tetrahedron 2001, 57, 915–945.
6. Ono, N. In The nitro group in organic synthesis; Feuer, H.,
Ed.; Wiley: New York, 2001.
4.3.8. Methyl-7-hydroxy-6-nitrododecanoate (5fb). Yield
77% of yellow oil; IR (cm21, neat) 1371, 1556, 1731, 3497;
1H NMR d (ppm) 0.83–0.97 (m, 3H), 1.22–1.91 (m, 12H),
1.92–2.21 (m, 2H), 2.27–2.39 (m, 2H), 2.44–2.51 (m,
0.5H), 2.58–2.62, (m, 0.5H), 3.65 (s, 3H), 3.77–3.91 (m,
0.5H), 3.92–4.02 (m, 0.5H), 4.32–4.49 (m, 1H); 13C NMR
d (ppm) 14.1, 22.7, 24.4, 25.1, 25.4, 25.7, 27.9, 30.2, 33.4,
33.7, 33.8, 51.8, 72.2, 72.5, 92.3, 92.9, 173.9, 174.0. Anal.
calcd for C13H25NO5 (275.34) C, 56.71; H, 9.15; N, 5.09.
Found: C, 56.84; H, 9.03; N, 4.98.
7. Ballini, R.; Bosica, G. Recent research development in
organic chemistry; Transworld Research Network:
Trivandrum, 1997; Vol. 1. pp 11–24.
8. Jouglet, B.; Bianco, L.; Rousseau, G. Synlett 1991, 907–908.
9. Sera, A.; Takagi, K.; Katayama, H.; Yamada, H. J. Org. Chem.
1988, 53, 1157–1161.
10. Misuri, Y.; Bulman, R. A.; Matsumoto, W. Heterocyclic 2002,
56, 599–606.
4.3.9. 1-(1-Nitrocyclopentyl)-1-butanol (5ig). Yield 83%
1
of colourless oil; IR (cm21, neat) 1357, 1537, 3445; H
11. Amato, I. Science 1993, 259, 1538–1541.
12. Illman, D. L. Chem. Engng News 1993, 71, 5–6.
13. Illman, D. L. Chem. Engng News 1994, 72, 22–27.
14. Rosini, G.; Ballini, R.; Petrini, M.; Sorrenti, P. Synthesis 1985,
515–517.
NMR d (ppm) 0.92 (t, 3H, J¼7.0 Hz), 1.22–1.91 (m, 9H),
2.03–2.20 (m, 1H), 2.37–2.62 (m, 3H), 3.79–3.91 (m, 1H);
13C NMR d (ppm) 14.0, 19.7, 24.8, 25.0, 33.8, 34.7, 35.6,
75.7, 103.8. Anal. calcd for C9H17NO3 (187.24) C, 57.73; H,
9.15; N, 7.48. Found: C, 57.89; H, 9.27; N, 7.33.
15. Bandgar, B. P.; Zirange, M. B.; Wadgaonkar, P. P. Synlett
1996, 149–150.
4.3.10. (E)-2-Nitro-1-phenyl-6-dodecen-3-ol (5ji). Yield
86% of yellow oil; IR (cm21, neat) 1377, 1560, 1605, 3031,
3066, 3544; 1H NMR d (ppm) 0.9 (t, 3H, J¼6.9 Hz), 1.21–
1.39 (m, 6H), 1.57–1.71 (m, 2H), 1.93–2.05 (m, 2H), 2.09–
2.30 (m, 2H), 2.38–2.42 (m, 0.5H), 2.48–2.53, (m, 0.5H),
3.13–3.38 (m, 2H), 3.83–3.94 (m, 0.5H), 4.08–4.17 (m,
0.5H), 4.68–4.77 (m, 1H), 5.30–5.59 (m, 2H), 7.16–7.37
(m, 5H); 13C NMR d (ppm) 14.3, 22.7, 28.7, 28.9, 29.3,
31.6, 32.7, 33.1, 33.8, 34.6, 36.8, 71.1, 72.1, 93.6, 93.7,
127.6, 127.7, 129.0, 129.1, 132.6, 132.8, 135.3, 136.0. Anal.
calcd for C18H27NO3 (305.42) C, 70.79; H, 8.91; N, 4.59.
Found: C, 70.91; H, 9.01; N, 4.47.
16. Tanaka, K.; Toda, F. Chem. Rev. 2000, 100, 1025–1074.
17. Gareth, W. V. C.; Raston, C. L.; Scott, J. L. Chem. Commun.
2001, 2159–2169.
18. Ballini, R.; Petrini, M.; Rosini, G. Synthesis 1987, 711–713.
19. Mdoe, J. E. G.; Clark, J. H.; Macquarrie, D. J. Synlett 1988,
625–627.
20. Ballini, R.; Bosica, G. Tetrahedron Lett. 1996, 8027–8030.
21. Ballini, R.; Bosica, G. Eur. J. Org. Chem. 1998, 355–358.
22. Goosen, A.; Morgan, D. J. Chem. Soc., Perkin Trans. 2 1994,
557–562.
23. Ballini, R.; Bosica, G.; Marcantoni, E.; Vita, P.; Batoli, G.
J. Org. Chem. 2000, 5854–5857.
24. Rozen, S.; Bar-Haim, A.; Mishani, E. J. Org. Chem. 1994,
1208–1209.
4.3.11. Ethyl-3-hydroxy-2-nitropropanoate (5kh). Yield