Selective synthesis of β-hydroxy nitroethanol ethers by alcoholysis of oxiranes

Article abstract of DOI:10.1080/00397910701557606

β-Hydroxy nitroethanol ethers are prepared by selective alcoholysis of oxiranes. The best results are obtained using a clay (monmorillonite K10) or a π-acid (TCNE) as the catalyst. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910701557606

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Selective Synthesis of β‐Hydroxy Nitroethanol
Ethers by Alcoholysis of Oxiranes
a
a
b
Jean‐Louis Gras , Mourad Daoubi & Isidro G. Collado
a
Faculty of Sciences St. Jerome, CNRS‐UMR, P. Cézanne University,
Marseille Cedex, France
b
Faculty of Sciences, Department of Chemistry, Cádix University, Puerto
Real, Cádix, Spain
Version of record first published: 05 Oct 2007
To cite this article: Jean‐Louis Gras, Mourad Daoubi & Isidro G. Collado (2007): Selective Synthesis of
β‐Hydroxy Nitroethanol Ethers by Alcoholysis of Oxiranes, Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic Chemistry, 37:20, 3589-3598
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Synthetic Communications , 37: 3589–3598, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701557606
Selective Synthesis of b-Hydroxy
Nitroethanol Ethers by Alcoholysis
of Oxiranes
Jean-Louis Gras and Mourad Daoubi
Faculty of Sciences St. Jerome, CNRS-UMR, P. C e´ zanne University,
Marseille Cedex, France
Isidro G. Collado
Faculty of Sciences, Department of Chemistry, C a´ dix University,
Puerto Real, C a´ dix, Spain
Abstract: b-Hydroxy nitroethanol ethers are prepared by selective alcoholysis of
oxiranes. The best results are obtained using a clay (monmorillonite K10) or a
p-acid (TCNE) as the catalyst.
Keywords: alcoholysis, nitroethanol ethers, oxiranes, TCNE
INTRODUCTION
The addition of alcohols to epoxides is a common synthetic process leading to
b-hydroxy ethers and vic-diol mono ethers. This general reaction can be done
under various experimental conditions, for instance, under basic conditions to
[1]
generate the alcoholate by using a polymer-supported amine (PSTBD) and
[
2,3]
under acid catalysis using TsOH. The reaction also can proceed through
an electron-transfer reaction using reagents such as cerium ammonium
[
4,5]
[6]
nitrate (CAN) or 2-3-dichloro-5,6-dicyano-p-benzoquinone (DDQ).
The search for milder experimental conditions and efficacy led to many
Received in Poland October 5, 2006
Address correspondence to Jean-Louis Gras, Faculty of Sciences St. Jerome,
CNRS-UMR, P. C e´ zanne University, F-13397, Marseille Cedex 20, France. E-mail:
jean-louis.gras@univ-cezanne.fr
3
589

3
590
J.-L. Gras, M. Daoubi, and I. G. Collado
III
investigations on the use of a Lewis acid catalyst, such as, for instance, an Fe
[10]
[
porphyrin complex, Fe(CF COO) , BiCl3, salen Co,
7]
[8]
[9]
[11]
Yb(OTf)3,
3
3
[
12]
[13]
[14]
[15]
Sc(OTf)3,
CeCl3,
CuBF4,
or (ClBu Sn) O.
2
2
In the course of our studies on the bioactivity of terpene-related
compounds, we were interested in introducing the nitroethoxy radical onto
specifically designed structures. Ring opening of an epoxide by 2-nitroethanol
appeared among the most convenient and versatile strategies to reach that goal.
However, the chemical nature of the nitro function limits the choice of the
reagent and reaction conditions. For instance, standard basic conditions are
ruled out because of the formation of a reactive nitronate anion. In addition,
the alcoolate of the expected alcohol might further compete with nitroethanol
to react with the epoxide. Radical reactions are of little interest because of the
difficulty in controlling the process, as shown by the reaction involving CAN
that led to the formation of polymers. Acidic conditions were first investigated
[
2,6–18]
in Russian laboratories
with some moderate success that can hardly be
generalized. Low yields and polycondensation plagued the use of this simple
route to more complex molecules.
The use of tetracyanoethylene (TCNE), a mild p-acid, turned out to effi-
[3,19,20]
ciently catalyze ring opening of epoxides by alcohols, mostly methanol.
This method was put in use in the cleavage of caryophyllene oxide by nitroetha-
[21,22]
nol along with a rearrangement of the terpene skeleton.
In this article, we report on the specific alcoholysis of oxiranes by
nitroethanol, under several reaction conditions designed to limit the overall
reaction to monocondensation, and give a general view on the scope and
limits of this general reaction.
Basic Conditions
The condensation of the alcoolate of nitroethanol, formed with Na, NaH, and
1,4-diazabicyclo[2.2.2]octane (DABCO), led to no reaction at room tempera-
ture, then to a rapid polymerization upon heating.
We turned toward polymer-supported bases such as a polyaminophospha-
zene on polystyrene, a strong neutral nitrogen base, with no result. Finally, the
reaction of various epoxides in nitroethanol (2 equivalents) at 608C activated
with 20% in weight of DOWEX monosphere 550A (OH) anion exchange
resin, a strongly basic (type I) anion, afforded the expected b-hydroxy ether
(
Scheme 1). This reaction uses no solvent, is clean, and gives the correspond-
ing diol as a main side product. Results are shown in Table 1. Using a solvent
such as dry THF led to little reaction after 4 days under reflux, and refluxing in
higher boiling dry dioxane gave only the corresponding diol.
Yields were not optimized, and it is noteworthy that the regioselectivity
was excellent in this addition. Addition of nitroethanol occurred at the most
substituted carbon on the oxirane. Because limonene oxide was used as a
mixture of stereomers, 9 should arise from the major isomer having the

b-Hydroxy Nitroethanol Ethers
3591
Scheme 1.
oxirane trans to the isopropylidene group. Diol 10 mainly arises from the
cleavage of the corresponding cis isomer on the least substituted carbon,
probably due to the size of the resin. The stereochemistry of 10 is based on
1
the coupling constants measured in the H NMR spectra. Ether 9 was contami-
nated by a minor regioisomer.
Brønsted Acids
Brønsted acids have been used in the alcoholysis of epoxides, and we refluxed
.
cyclohexenoxide in CH Cl along with p-TsOH H O (0.05 equivalent) for
2
2
2
4
h to obtain a complex mixture of compounds. At room temperature, the
reaction was much cleaner and complete after 48 h, affording ether 11 as
the main product. No or little expected addition of nitroethanol occurred,
and we observed the simple hydrolysis of cyclohexene oxide followed by con-
densation onto a second epoxide (Scheme 2).
This strategy thus turned out to be of little interest when applied to
nitroethanol.
Lewis Acids
The use of Lewis acids provides a mild method for the alcoholysis of epoxides,
but there is no reagent that can be generally applied to all cases. Rather, there
Table 1. Reaction of epoxides with 2-nitroethanol activated by Dowex, 20% in
weight
Epoxide
Time
Products, yield (%)
1
,2-Epoxy-5-hexene
Styrene oxide
,2-Epoxy-3-phenoxypropane
3 d
2 d
1: hex-5-ene-1,2-diol, 55; 2, 10
3, 57; 4, 38
5, 40; 6, 42
1
2.5 d
2 d
Cyclohexene oxide
Limonene oxide
7, 52; 8, 38
9, 45; 10, 37
3 d

3
592
J.-L. Gras, M. Daoubi, and I. G. Collado
Scheme 2.
is a set of candidates from which an appropriate acid might solve a given
problem. The reaction usually gives a mixture of regioisomers.
.
Strong Lewis acids such as BF3 Et O gave a complex mixture of
2
products, even at low temperature (2788C) and low catalyst concentration
(5%). Milder Lewis acids such as Yb(OTf) also led to the same complex
mixture of products, synthetically useless.
Finally, styrene oxide reacted with nitroethanol (3 equivalents) at rt for
3
.
30 h in the presence of CeCl3 7H O to give both regioisomers with the
2
secondary ether favored. Anhydrous CeCl led to the same result albeit
3
much faster (3 h). An even faster addition was obtained using BiCl (5%),
3
leading to hydroxyether 3 in 45% yield. The reaction alternatively can be
run at 08C for 72 h in CH Cl as the solvent with the same result (Scheme 3).
This positive result encouraged us to investigate even milder acids such as
2
2
clays and p-acids.
Clays and p-Acids
Montmorillonite K is a mineral adsorbent that promotes reactions catalyzed by
Brønsted or Lewis acids, and TCNE is a p-acid that has been used for the
methanolysis of epoxides. Both reagents gave satisfactory results in the
addition of nitroethanol to most of the epoxides that were involved: alkyl,
ring fused, and functionalized.
The additions were run at room temperature without solvent, using
instead 3 equivalents of nitroethanol, and they are followed by an easy
workup. Results are gathered in Table 2 and Scheme 4.
Under those conditions, the reaction is rather highly regioselective,
favoring the addition of nitroethanol on the most substituted carbon atom of
the oxirane, except for isophorone oxide (entries 15 and 16). In that case,
the addition mainly leads to C-a substitution, and the anti-b-
Scheme 3.

b-Hydroxy Nitroethanol Ethers
3593
Table 2. K10- and TCNE-catalyzed reaction of epoxides with 2-nitroethanol
Epoxide
Entry Catalyst Time (h) Products, yield (%)
a
a
1
1
1
,2-Epoxy propane
,2-Epoxy butane
,2-Epoxy-5-hexene
1
2
3
4
5
6
7
8
9
0
K10
TCNE
K10
4
12, 10
12, 15
3
3
13, 36; 14, 18
13, 37; 14, 15
15, 58; 16, 34
15, 58
TCNE
K10
6
28
28
3.5
4
TCNE
K10
Styrene oxide
,2-Epoxy-3-phenoxypropane
3, 98
3, 84
TCNE
K10
1
48
44
4
5, 92
5, 96
1
TCNE
K10
Cyclohexene oxide
Limonene oxide
Isophorone oxide
11
7, 60
7, 58
12
13
TCNE
K10
18
1.5
18
22
24
24
24
b
9, 65; 17, 15
b
14
15
TCNE
K10
9, 31; 17, 8; 18, 9
19, 36; 20, 10
19, 30; 20, 10
1
6
TCNE
K10
K10
b
2
5
6
17
18
21, 20; 22, 60
b
23, 19; 24, 58
2
a
b
Volatile compound that was simply characterized.
Stereochemistry not attributed.
hydroxycompound 19 is obtained as the major regioisomer. This latter regios-
electivity applied to the terpene-like compound 25 shown in entry 17. The
addition of nitroethanol was accompanied with opening of the oxirane,
followed by dehydration and conjugation to enone 22 (epi pulegonacetone).
Scheme 4.

3
594
J.-L. Gras, M. Daoubi, and I. G. Collado
In entry 18, the addition to 26 is accompanied by hydrolysis of the oxirane,
leading to olefine 22 after dehydration of the tertiary alcohol.
CONCLUSION
The nitroethanol monoethers of some vic-diols are of some biological interest,
and they can be synthesized by ring opening of epoxides. If needed, the
reaction can be done with acceptable yields under basic conditions using a
DOWEX resin. CeCl and BiCl were among the few Lewis acids to reason-
3
3
ably afford the expected ethers. Most satisfactory results were obtained using
either montmorillonite K or TCNE as the catalyst. The experimental
procedure is simple, and the reaction proved highly regioselective, mostly
giving addition onto the most substituted carbon of the epoxide.
EXPERIMENTAL
Typical Procedure for the Alcoholysis of Epoxides
The catalyst (montmorillonite or TCNE) is added to a solution of the epoxide
in nitroethanol (3 equiv.) under Ar. The mixture is magnetically stirred at
room temperature until the epoxide has vanished. After dilution with
CH Cl , the medium is neutralized by addition of solid NaHCO . The
2
2
3
solution is filtered off and concentrated under vacuum to afford a crude
product from which isomers are further purified by column chromatography
over silica gel.
Diols 1, 4, 6, and 8 are identical to the commercially available
compounds.
Data
1
Dioxane 2: H NMR (300 MHz, CDCl ): 5.80 (1H, ddt, J ¼ 17.2, 10.3, 6.6);
3
5
.08 (1H, dd, J ¼ 17.2, 1.6); 5.02 (1H, dd, J ¼ 10.2, 1.6); 4.42 (1H, dd,
J ¼ 8.0, 7.5); 4.40 (1H, d, J ¼ 7.2); 4.34 (1H, m); 2.70 (OH, bs); 2.25 (2H,
1
m); 1.60 (2H, m). C NMR (50.3, CDCl ): 137.6; 116.6; 81.1; 68.68; 33.3;
3
3
29.9. Anal. calcd. for C H O (%): C, 73.43; H, 10.27. Found: C, 73.36;
H, 10.37.
12 20 2
1
b-Hydroxy nitroethanol ether 3: H NMR (300 MHz, CDCl ): 7.45–7.25 (5H,
3
m); 4.55 (2H, m); 4.49 (1H, dd, J ¼ 8.5, 3.6); 3.94 (2H, m); 3.72 (1H, dd,
1
3
J ¼ 12.0, 8.3); 3.62 (1H, dd, J ¼ 12.0, 3.8); 2.30 (OH, bs). C NMR (50.3,
CDCl ): 137.9; 129.3; 129.1; 127.4; 84.2; 75.8; 67.4; 65.0. Anal. calcd. for
3
C H NO (%): C, 50.87; H, 6.20; N, 6.63. Found: C, 50.79; H, 6.30, N, 6.58.
0
1
13
4

b-Hydroxy Nitroethanol Ethers
3595
1
b-Hydroxy nitroethanol ether 5: H NMR (300 MHz, CDCl ): 7.30 (2H, m);
3
7
.00 (1H, m); 6.92 (2H, m); 4.56 (2H, m); 4.14 (1H, m); 4.08 (2H, AB,
J ¼ 5.4); 4.03 (2H, dd, J ¼ 6.6); 3.74 (1H, dd, J ¼ 10.0, 4.5); 3.68 (1H, dd,
1
3
J ¼ 10.0, 5.2); 2.60 (OH, bs). C NMR (50.3, CDCl ): 158.8; 129.9; 121.6;
3
1
14.9; 75.3; 72.6; 69.4; 68.9; 67.0. Anal. calcd. for C H NO (%): C,
6 13 4
4
4.17; H, 8.03; N, 8.58. Found: C, 44.01; H, 8.13, N, 8.52.
1
b-Hydroxy nitroethanol ether 15: H NMR (300 MHz, CDCl ): 5.80 (1H, m);
3
5
.01 (1H, d, J ¼ 18.7); 4.96 (1H, d, J ¼ 10.2); 4.12 (2H, m); 3.65 (1H, dd,
J ¼ 11.0, 2.5); 3.50 (1H, dd, J ¼ 11.0, 6.3); 3.43 (1H, m); 2.51 (OH, bs);
1
.06 (2H, m); 1.61 (2H, m). C NMR (50.3, CDCl ): 138.5; 115.9; 81.03;
3
2
7
7
3
6.0; 65.8; 65.1; 30.5; 30.0. Anal. calcd. for C H NO (%): C, 50.78; H,
8
15
4
.99; N, 7.40. Found: C, 50.71; H, 8.09; N, 7.43.
1
b-Hydroxy nitroethanol ether 16: H NMR (300 MHz, CDCl ): 5.76 (1H, m);
3
5
3
2
7
7
.01 (1H, d, J ¼ 18.7); 4.94 (1H, d, J ¼ 10.2); 4.50 (2H, m); 4.07 (1H, m);
.67 (1H, dd, J ¼ 11.0, 2.5); 3.60 (1H, dd, J ¼ 11.0, 6.3); 2.51 (OH, bs);
1
.11 (2H, m); 1.51 (2H, m). C NMR (50.3, CDCl ): 138.4; 115.4; 76.0;
3
3
0.0; 67.0; 59.0; 32.4; 30.0. Anal. calcd. for C H NO (%): C, 50.78; H,
8
15
4
.99; N, 7.40. Found: C, 50.74; H, 8.03; N, 7.38.
1
b-Hydroxy nitroethanol ether 7: H NMR (300 MHz, CDCl ): 4.56 (2H, m);
3
4
.16 (1H, ddd, J ¼ 10.0, 7.0, 3.0); 3.98 (1H, ddd, J ¼ 10.0, 6.6, 3.5); 3.41
1
3
(
1H, m); 3.11 (1H, m); 2.70 (OH, bs); 2.01 (4H, m); 1.68 (4H, m).
C
NMR (50.3, CDCl ): 85.2; 76.2; 74.3; 65.2; 32.9; 29.8; 24.8; 24.5. Anal.
3
calcd. for C H NO (%): C, 50.78; H, 7.99; N, 7.40. Found: C, 50.75; H,
8
15
4
8
.03; N, 7.41.
1
b-Hydroxy nitroethanol ether 9: H NMR (300 MHz, CDCl ): 4.69 (2H, bs);
3
4
.49 (2H, m, J ¼ 5.1); 3.88 (2H, dd, J ¼ 5.3); 3.64 (1H, bs); 2.23 (1H, m,
J ¼ 11.7); 1.83 (2H, m, J ¼ 13.0, 2.7); 1.69 (3H, s); 1.7–1.21 (5H, m);
1
.19 (3H, s). C NMR (50.3, CDCl ): 150.2; 109.7; 76.7; 76.5; 72.8; 57.8;
3
1
3
5
3
8.0; 34.4; 29.9; 26.5; 21.4; 21.3. Anal. calcd. for C H NO (%): C,
1
2
21
4
9.24; H, 8.70; N, 5.76. Found: C, 59.17; H, 8.74, N, 5.72.
1
b-Hydroxy nitroethanol ether 17: H NMR (300 MHz, CDCl ): 4.71 (2H, bs);
3
4
1
8
.55 (2H, m, J ¼ 5.1); 4.10–3.90 (2H, m); 3.21 (1H, bs); 2.25 (1H, m); 2.0–
1
.0 (6H, m); 1.74 (3H, s); 1.17 (3H, s). C NMR (50.3, CDCl ): 149.1; 109.3;
3
3
2.9; 76.2; 71.1; 57.8; 37.8; 35.3; 28.4; 26.4; 21.7; 15.5. Anal. calcd. for
C H NO (%): C, 59.24; H, 8.70; N, 5.76. Found: C, 59.15; H, 8.76, N, 5.71.
1
2
21
4
1
3
b-Hydroxy nitroethanol ether 18: C NMR (50.3, CDCl ): stereomers,
3
selected signals: 148.7; 109.5; 79.6.
1
b-hydroxy nitroethanol ethers 12: H NMR (300 MHz, CDCl ): 4.50 (2H, m);
3
3
.95 (2H, m); 3.40 (4H, m); 1.14 (3H, m).
1
b-Hydroxy nitroethanol ether 13: H NMR (300 MHz, CDCl ): 4.56 (2H, m);
3
4
.18 (1H, m); 4.05 (1H, m); 3.70 (2H, m); 3.50 (OH); 3.30 (1H, m); 1.50

3
596
J.-L. Gras, M. Daoubi, and I. G. Collado
1
2H, m); 0.95 (3H, m). C NMR (50.3, CDCl ): 81.0; 77.6; 66.9; 64.7; 19.9;
3
(
3
1
4
5.9. Anal. calcd. for C H NO (%): C, 44.17; H, 8.03; N, 8.58. Found: C,
6 13 4
4.10; H, 8.09, N, 8.56.
1
b-Hydroxy nitroethanol ether 14: H NMR (300 MHz, CDCl ): 4.53 (2H, m);
3
1
.13 (2H, m); 3.50 (6H, m); 1.50 (2H, m); 0.95 (3H, m). C NMR (50.3,
3
4
CDCl ): 76.9; 75.8; 66.8; 65.8; 19.8; 18.8. Anal. calcd. for C H NO (%):
C, 44.17; H, 8.03; N, 8.58. Found: C, 44.11; H, 8.08, N, 8.56.
3
6
13
4
1
Diol 10: H NMR (300 MHz, CDCl ): 4.73 (2H, bs); 3.63 (1H, dd, J ¼ 3.5,
3
3
1
7
7
.3); 2.26 (1H, m); 1.93 (1H, ddd, J ¼ 14.0, 11.7, 2.8); 1.79–1.49 (7H, m);
1
.73 (3H, s); 1.27 (3H, s). C NMR (50.3, CDCl ): 149.7; 109.3; 74.3;
3
3
1.6; 37.8; 34.4; 34.0; 28.1; 26.6; 21.4. Anal. calcd. for C H O (%): C,
1
0 18 2
0.55; H, 10.66. Found: C, 70.45; H, 10.71.
1
b-Hydroxy nitroethanol ether 19: H NMR (300 MHz, CDCl ): 4.54 (1H, ddd,
3
J ¼ 13.4, 6.0, 4.1); 4.47 (1H, ddd, J ¼ 13.4, 6.0, 4.2); 4.23 (1H, s), 3.6 (OH);
2
1
.35 (1H, d, J ¼ 13.3); 2.25 (1H, dd, J ¼ 13.3, 2.3); 1.95 (1H, d, J ¼ 14.4);
1
3
.80 (1H, dd, J ¼ 14.3, 2.3); 1.14 (3H, s); 1.12 (3H, s); 0.93 (3H, s).
C
NMR (50.3, C D ): 208.8; 81.6; 81.5; 75.8; 59.3; 50.7; 49.0; 33.2; 32.9;
6
6
27.4; 18.3. Anal. calcd. for C H NO (%): C, 53.87; H, 7.81; N, 5.71.
Found: C, 53.84; H, 7.83; N, 5.68.
11 19 5
1
b-Hydroxy nitroethanol ether 20: H NMR (300 MHz, CDCl ): 4.53 (2H, m);
3
4
.13 (2H, m); 4.02 (1H, s); 3.40 (OH); 2.32 (1H, d, J ¼ 8.0); 2.26 (1H, d,
J ¼ 9.0); 1.85 (1H, d, J ¼ 15.2); 1.70 (1H, d, J ¼ 15.2); 1.42 (3H, s); 1.06
1
3
(
3H, s); 0.99 (3H, s). C NMR (50.3, CDCl ): 209.3; 82.9; 82.1; 76.3;
3
6
5
0.8; 52.6; 36.7; 34.4; 28.4; 22.9. Anal. calcd. for C H NO (%): C,
11 19 5
3.87; H, 7.81; N, 5.71. Found: C, 53.81; H, 7.86, N, 5.67.
1
b-Hydroxy nitroethanol ether 21 (mixture of diastereomers): H NMR
300 MHz, CDCl ) (selected signals): 4.6 (2H, m); 4.25 (2H, m); 4.0 (1H, s);
(
3
3
.4 (OH); 2.25 (1H, d, J ¼ 14); 2.45 (H, d, J ¼ 13); 2.34 (H, d, J ¼ 14); 2.19
1
3
(
(
(
(
1H, d, J ¼ 13); 1.02 (3H, s); 0.94 (3H, d, J ¼ 13); 0.91 (3H, s). C NMR
50.3, CDCl ): 210.2 (211.4); 86.5 (81.7); 76.7 (76.4); 76.6 (75.8); 61.6
3
59.9); 50.3 (49.6); 50.0 (44.2); 46.4 (39.8); 39.5 (35.1); 31.9 (31.5); 30.0
31.2); 27.4 (28.2); 26.6 (26.9); 22.8 (25.5); 20.6 (18.0). Anal. calcd. for
C H NO (%): C, 60.18; H, 8.42; N, 4.68. Found: C, 60.14; H, 8.46, N, 4.65.
1
5
25
5
1
Enone 22: H NMR (300 MHz, CDCl ): 5.9 (1H, d, J ¼ 5.7); 2.3 (1H, m); 2.2
3
(
1H, m); 1.8 (1H, dd, J ¼ 12.4, 3.2); 1.7 (1H, m); 1.6 (2H, m); 1.52 (1H, dd,
J ¼ 12.4, 3.2); 1.4 (1H, m); 1.2 (2H, m); 1.14 (3H, s); 1.04 (3H, s); 0.97 (3H, d,
1
3
J ¼ 6.7). C NMR (50.3, CDCl ): 198.0; 145.0; 130.2; 48.9; 45.2; 35.5; 35.4;
3
3
5.0; 32.8; 29.6; 27.4; 23.2; 22.3. Anal. calcd. for C H O (%): C, 81.20; H,
13 20
10.48. Found: C, 81.23; H, 10.52.
1
b-Hydroxy nitroethanol ether 23: H NMR (300 MHz, CDCl ): 5.22 (1H, ddd,
3
J ¼ 12.6, 4.3, 2.8); 4.0 (1H, m); 3.99 (OH); 3.99 (1H, m); 3.96 (1H, m); 2.12

b-Hydroxy Nitroethanol Ethers
3597
(
1H, m); 2.06 (3H, s); 1.99–1.10 (7H, m); 1.17 (3H, s); 0.91 (3H, s); 0.87 (3H,
1
3
d, J ¼ 6.4). C NMR (50.3, CDCl ): 170.6; 80.6; 76.2; 74.0; 71.8; 57.1; 47.9;
3
44.7; 35.0; 34.7; 34.1; 31.6; 31.1; 29.6; 26.6; 23.3; 21.6. Anal. calcd. for
C H NO (%): C, 59.46; H, 8.51; N, 4.08. Found: C, 59.41; H, 8.54; N, 4.05.
1
7
29
6
1
Alcohol 24: H NMR (300 MHz, CDCl ): 5.68 (1H, bs); 5.02 (1H, ddd,
3
J ¼ 12.3, 4.7, 2.4); 3.86 (1H, bs); 2.47 (1H, m); 2.14 (1H, m); 2.04 (3H, s);
1
.97 (1H, m); 1.77–0.90 (6H, m); 1.10 (3H, s); 1.08 (3H, s); 0.88 (3H, d,
1
3
J ¼ 6.6). C NMR (50.3, CDCl ): 170.7; 139.7; 121.8; 74.1; 73.0; 39.4;
3
36.5; 35.2; 34.8; 33.4; 29.1; 27.8; 26.1; 21.6; 20.8. Anal. calcd. for
C H O (%): C, 71.39; H, 9.59. Found: C, 71.62; H, 9.62.
1
5
24
3
1
Diol 11: H NMR (300 MHz, CDCl ): 4.27 (2H, m); 3.59 (2H, m); 3.33 (OH);
3
1
.99 (4H, m); 1.65 (4H, m); 1.20 (8H, m). C NMR (50.3, CDCl ): 86.7; 72.0;
3
1
3
3
Found: C, 67.23; H, 10.36.
2.3; 30.8; 23.9; 23.2. Anal. calcd. for C H O (%): C, 67.26; H, 10.35.
1
2 22 3
ACKNOWLEDGMENT
We are grateful to the Agence Universitaire de la Francophonie for a research
grant given to M. D.
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2