Journal of Oleo Science

Copyright ©2008 by Japan Oil Chemists’ Society

J. Oleo Sci. 57, (8) 437-443 (2008)

An Efficient Synthesis of Five-membered

Cyclic Ethers from 1,3-Diols Using Molecular
Iodine as a Catalyst
Yoshio Kasashima1＊, Hiroshi Fujimoto2, Takashi Mino3, Masami Sakamoto3 and
Tsutomu Fujita3
1
Education center, Faculty of engineering, Chiba Institute of Technology (Shibazono 2-1-1, Narashino-shi, Chiba 275-0023, JAPAN)
2
Graduate School of Science and Technology, Chiba University
3
Graduate School of Engineering, Chiba University

Abstract: Intramolecular cyclic etherification of 1,3-diols was investigated using iodine as a catalyst under
solution reaction conditions. Compounds containing five-membered ether rings were obtained. Propella
ether (11-oxatricyclo[4.4.3.0 1 , 6 ]tridecane) was conveniently synthesized from 1,3-diol (6-(2-
hydroxyethyl)spiro[4.5]decan-6-ol) in 97% yield via carbon skeleton rearrangement. Spiroethers and
bicyclic ethers were also obtained from the corresponding 1,3-diols in yields of over 77%. The most
suitable reaction conditions were a temperature of 80℃, a 1:0.2 molar ratio of 1,3-diol:iodine, and a time
period of 8 h. In addition, terpenoic ethers were efficiently synthesized from the corresponding 1,3-diols,
derived from (+)-camphor and (–)-fenchone, via skeleton rearrangement. In particular, the reaction of the
1,3-diol derived from (+)-camphor proceeded smoothly at room temperature with a yield of 91%. The yield
of the cyclic ether using iodine as a catalyst was comparable to the method using sulfuric acid.

Key words: iodine; five-membered ether ring; 1,3-diol; etherification

1 INTRODUCTION addition, iodine has been used as an efficient catalyst in

Cyclic ether compounds are frequently used in perfumes,
and the synthesis of cyclic ether compounds is particularly
important to the chemical industry. Notably, while six-
membered rings can be formed easily, derivation of unsta-
ble five-membered cyclic ethers from 1,3-diols is difficult.
However, it was recently repor ted that efficient
intramolecular cyclization of 1,3-diols was accomplished to
provide the corresponding five-membered cyclic ethers
using strong acids, such as sulfuric acid, potassium hydro-
gensulfate, and p-toluenesulfonic acid, as catalysts1-4). Fur-
thermore, palladium compounds5,6), triphenylphosphine7)
and a selenium compound8) were also found to be effective
catalysts in the cyclization of 1,3-diols. However, these cat-
alysts are very expensive and/or toxic. Therefore, in this
study, iodine was investigated as a catalyst in the
intramolecular cyclization of 1,3-diols. Iodine is easy to
handle and has low toxicity. Upon completion of the reac-
tion, iodine can be removed easily by sodium thiosulfate. In
several organic reactions9-21). Kim et al. reported that lac-
tones were obtained from bulky unsaturated carboxylic
acids without iodination22). We previously reported the lac-
tonization of the bulky 3-hydroxy acids derived from (+)-
camphor and (–)-fenchone using iodine as a catalyst23).
2 EXPERIMENTAL
2.1 General
NMR spectra were obtained using a 400 or 500 MHz FT-
NMR spectrometer (JEOL JNM-LA-400 or JNM-LA-500)
with an internal standard. IR spectra were recorded on a
JASCO FT/IR-230 spectrometer. Mass spectra were
recorded on a JEOL JMS-HX110A and JEOL JMS-AX500.
Optical rotations were measured on a JASCO DIP-370 .

＊
Correspondence to: Yoshio Kasashima, Education center, Faculty of engineering, Chiba Institute of Technology, Shibazono 2-1-1,
Narashino-shi, Chiba 275-0023, JAPAN
E-mail: yoshio.kasashima@it-chiba.ac.jp
Accepted April 10, 2008 (received for review March 14, 2008)
Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online
http://www.jstage.jst.go.jp/browse/jos/

437
 Y. Kasashima, H. Fujimoto, T. Mino et al.

1
2.2 Materials H-NMR (d,CDCl3): 1.32-1.62 (16H, m), 1.83 (2H, t, J=7.5 Hz),
1,3-Diols, 3.94 (2H, t, J=7.5 Hz),
13
6-(2-hydroxyethyl)spiro[4.5]decan-6-ol 1a C-NMR (d,CDCl3): 22.2, 23.3, 32.9, 33.3, 36.5, 42.2, 63.2,
1-(2-hydroxyethyl)spiro[5.5]undecan-1-ol 1b 81.6
1-(2-hydroxyethyl)spiro[4.4]nonan-1-ol 1c IR (neat, cm-1): 2931, 2860
3-(1-methylcyclopentyl)pentane-1,3-diol 3a HRMS calcd for C12H20O : 180.1514; found: m/z 180.1510.
3-(1-methylcyclohexyl)pentane-1,3-diol 3b
3-cyclopentylbutane-1,3-diol 5a 12-Oxatricyclo[5.4.3.01,7]tetradecane (2b)
1
3-cyclohexylbutane-1,3-diol 5b H-NMR (d,CDCl3): 1.04-1.69 (20H, m), 1.81 (2H, t, J=7.2 Hz),
2-(2-hydroxyethyl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol 7 3.79 (2H, t, J=7.2 Hz)
13
and C-NMR (d,CDCl3): 22.6, 23.2, 26.0, 31.7, 32.6, 37.6, 55.6,
2-(2-hydroxyethyl)-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol 9 63.4, 83.2
were prepared by reaction of the corresponding 3-hydroxy IR (neat, cm-1): 2931, 2864
acid using lithium aluminum hydride. A typical procedure HRMS calcd for C13H22O: 194.1671; found: m/z 194.1668.
is as follows:
To 1.14g (30 mmol) of lithium aluminum hydride in 7-Oxatricyclo[4.3.3.01,6]dodecane (2c)
1
120mL of tetrahydrofuran, 5.30g (25 mmol) of (6-hydrox- H-NMR (d,CDCl3): 1.21-1.83 (14H, m), 1.96-2.17 (2H, m),
yspiro[4.5]dec-6yl)-ethanoic acid in 100 mL of tetrahydrofu- 3.85-3.97 (2H, m)
13
ran was added over a period of 1 h with stirring at room C-NMR (d,CDCl3): 21.5, 22.1, 22.8, 31.8, 32.6, 35.8, 36.5,
temperature. It was refluxed for an additional 6 h, and 39.0, 50.5, 65.3, 91.6
cooled to room temperature. The reaction mixture was IR (neat, cm-1): 2929, 2864
decomposed 50 mL of iced-water and acidified with 10% HRMS calcd for C11H18O : 166.1358; found: m/z 166.1351.
sulphuric acid (100 mL). It was then extracted with 100 mL
of diisopropyl ether three times. The organic layer was 3a-Ethyl-7a-methyloctahydrobenzofuran (4a)
1
washed with 150 mL of water three times, dried with anhy- H-NMR (d,CDCl3): 0.87 (3H, t, J=7.5 Hz), 1.01 (3H, s), 1.22-
drous sodium sulfate, and evaporated. The residual oil was 1.82 (12H, m), 3.82-3.90 (2H, m)
13
flash-chromatographed on silica gel eluted with hexane/ C-NMR (d,CDCl3): 10.1, 22.2, 22.7, 23.1, 25.7, 29.8, 34.3,
ethyl acetate (8/1) to give 4.46g (22.5 mmol; 90% yield) of 36.1, 45.7, 63.5, 83.2
6-(2-hydroxyethyl)spiro[4.5]decan-6-ol 1a. IR (neat, cm-1): 2933, 2875
1
H-NMR (d,CDCl3): 1.29-1.95 (18H, m), 2.24 (1H, s), 3.00 (1H, HRMS calcd for C11H20O : 168.1514 ; found: m/z 168.1509 .
br-s), 3.73-3.78 (1H, m), 3.92-4.00 (1H, m)
13
C-NMR (d,CDCl3): 22.2, 22.9, 26.1, 26.5, 32.7, 33.9, 34.4, 3a-Ethyl-8a-methyloctahydrocyclohepta[b]furan (4b)
1
35.3, 35.7, 51.3, 60.0, 77.6 H-NMR (d,CDCl3): 0.89 (3H, s), 0.90 (3H, t, J=7.5 Hz), 1.06-
IR (KBr, cm-1): 3330, 2954 1.49 (5H, m), 1.52-1.70 (8H, m), 1.81-1.93 (1H, m), 3.73-3.80
m.p. 105.5-106.5℃. (2H, m)
13
C-NMR (d,CDCl3): 10.1, 20.3, 22.7, 23.4, 26.5, 28.8, 30.8,
2.3 Etherification 31.6, 37.9, 46.6, 63.4, 84.8
A typical procedure is as follows: IR (neat, cm-1): 2933, 2873
In a 50-mL flask were placed 500 mg (2.5 mmol) of 7, 157 HRMS calcd for C12H22O : 182.1671 ; found: m/z 182.1664.
mg (0.5 mmol) of iodine and 25ml of acetonitrile, and the
mixture was stirred at room temperature for 3 h. A 5% 4-Methyl-1-oxaspiro[4.4]nonane (6a)
1
aqueous solution of sodium thiosulfate (50 mL) was added H-NMR (d,CDCl3): 0.97 (3H, d, J=6.7 Hz), 1.47-1.77 (9H, m),
to the reaction mixture in order to remove iodine, and the 2.00-2.15 (2H, m), 3.70-3.84 (2H, m)
13
mixture was then extracted with 50 mL of diisopropyl C-NMR (d,CDCl3): 15.8, 24.1, 24.7, 32.2, 34.5, 37.3, 40.1,
ether three times. The organic layer was washed with 100 64.8, 93.9
mL of water three times, dried with anhydrous sodium sul- IR (neat, cm-1): 2958, 2871
fate, and evaporated. The product was purified by silica gel HRMS calcd for C9H16O : 140.1201 ; found: m/z140.1198.
column chromatography eluted with hexane/ethyl acetate
(10/1). A total of 410 mg (2.28 mmol; 91% yield) of 5,6,6- 4-Methyl-1-oxaspiro[4.5]decane (6b)
trimethyl-4-oxatricyclo[5.2.1.01,5]decane (8) was obtained. 1
H-NMR (d,CDCl3): 0.94 (3H, d, J=6.9 Hz), 1.14-1.27 (2H, m),
The spectroscopic data of the product agreed with those of 1.41-1.67 (9H, m), 1.78-1.86 (1H, m), 2.03-2.12 (1H, m), 3.70-
824). 3.86 (2H, m)
13
C-NMR (d,CDCl3): 15.1, 22.7, 23.8, 26.4, 30.7, 34.0, 36.6,
11-Oxatricyclo[4.4.3.01,6]tridecane (2a) 42.5, 64.8, 83.2

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J. Oleo Sci. 57, (8) 437-443 (2008)
 Synthesis of Five-membered Cyclic Ethers from 1,3-Diols

IR (neat, cm-1): 2931, 2860 [a] 25

D : -20.0 (c=1.00, CDCl3)
HRMS calcd for C10H18O : 154.1358 ; found: m/z154.1352. HRMS calcd for C12H20O : 180.1514 ; found: m/z180.1507.

5,6,6-Trimethyl-4-oxatricyclo[5.2.1.01,5]decane (8)
1
H-NMR (d,CDCl3): 0.94 (3H, s), 0.96 (3H, s), 1.02 (3H, s), 0.96-
1.00 (1H, m), 1.25-1.32 (1H, m), 1.38-1.54 (2H, m), 1.62-1.72 3 RESULTS AND DISCUSSION
(2H, m), 1.78-1.84 (1H, m), 1.87-1.97 (2H, m), 3.90 (1H, td, 1,3-Diols were prepared by reduction of the correspond-
J=8.3, 2.9 Hz), 3.97 (1H, q, J=7.7 Hz) ing 3-hydroxy acids using lithium aluminum hydride. In a
13
C-NMR (d,CDCl3): 17.0, 23.2,23.9, 24.8, 25.8, 28.7, 39.2, flask, a solvent, 1,3-diol 1a, and iodine were added and the
44.9, 49.7, 58.9, 66.4, 90.7 reaction mixture was stirred with heating. After the reac-
IR (KBr, cm-1): 2960, 2873 tion, the product was isolated. The spectroscopic data of
m.p. 85-87℃ the isolated product indicated the structure of propella
[a] 25
D : -18.1 (c=1.00, CDCl3) cyclic ether 2a, which was obtained from 1a by dehydration
HRMS calcd for C12H20O : 180.1514 ; found: m/z180.1520. and subsequent carbon skeleton rearrangement. Similarly,
propella cyclic ether 2b was obtained from 1b, and 2c from
5,10,10-Trimethyl-4-oxatricyclo[5.2.1.01,5]decane (10) 1c. The results are summarized in Table 1. Next, the opti-
1
H-NMR (d,CDCl3): 0.88 (3H, s), 1.14 (3H, s), 1.16 (3H, s), 1.14- mum conditions for the reaction of 1a were investigated.
1.35 (3H, m), 1.65-1.81 (5H, m), 2.26 (1H, dt, J=13.0, 3.1 Hz), The effect of the solvent under reflux conditions was
3.88-3.98 (2H, m) investigated using a molar ratio of the 1,3-diol:iodine of
13
C-NMR (d,CDCl3): 20.9, 21.1, 23.5, 24.2, 25.6, 26.4, 44.1, 1:0.2 and a reaction time of 8 h. Solvents used were ace-
46.6, 48.3, 59.9, 68.0, 89.9 tonitrile (entry 1), toluene (entry 4), xylene (entry 9),
IR (KBr, cm-1): 2945, 2871 dimethylformamide (entry 10), and hexane (entry 12). When
m.p. 116-117℃ toluene and hexane were used respectively, the yields were

Table 1 The Intramolecular Cyclization of 1,3-Diols 1a,b,c.

Entry m n Material Solvent I2 (eq.) Temp. (℃) Yield (%)
1 2 1 1a MeCN 0.2 reflux 5
2a 2 1 1a Toluene 0.2 r.t. 2
3 2 1 1a Toluene 0.1 reflux 67
4 2 1 1a Toluene 0.2 reflux 67
5 2 1 1a Toluene 0.5 reflux 60
6 2 1 1a Toluene 0.1 80 90
7 2 1 1a Toluene 0.2 80 84
8 2 1 1a Toluene 0.5 80 76
9 2 1 1a Xylene 0.2 reflux 53
10 2 1 1a DMF 0.2 170 39
11 2 1 1a Hexane 0.1 reflux 92
12 2 1 1a Hexane 0.2 reflux 97
13 2 1 1a Hexane 0.5 reflux 91
14 2 2 1b Hexane 0.2 reflux 76
15 1 1 1c Hexane 0.2 reflux 80

Conditions: 1,3-diol, 2.5 mmol; solvent, 25 mL; time, 8 h.

a
Stirred for 24 h.

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J. Oleo Sci. 57, (8) 437-443 (2008)
 Y. Kasashima, H. Fujimoto, T. Mino et al.
high. In particular, when hexane was used as the solvent,
the yield was 97%, indicating that iodination did not occur.
Although the product contains an unstable five-membered
ring, the reaction proceeded quantitatively. Therefore,
toluene and hexane were used in subsequent investiga-
tions. In the case of toluene, when the molar ratio of iodine
was increased to 1:0.5 (entry 5), the yield decreased to 60%.
When the molar ratio of iodine was decreased to 1:0.1
(entry 3), the yield was about the same. When the reaction
temperature was lowered to 80℃ and the molar ratio of
iodine was 1:0.1, the yield improved to 90% (entry 6). The
molar ratio of iodine was investigated using hexane as the
solvent (entries 11, 12, and 13). The yield was highest with
a molar ratio of 1:0.2 (entry 12). Using the conditions of
entry 12 in Table 1, the reactions of 1b and 1c were
attempted, respectively (entries 14 and 15). From 1b, pro-
pella cyclic ether 2b was obtained in 76% yield, and 2c was
obtained in 80% yield from 1c. Thus, iodine was shown to
be an efficient catalyst for the synthesis of five-membered
cyclic ethers from 1,3-diols.
The reaction of 1,3-diol 3a was carried out using iodine
as the catalyst. The spectroscopic data of the isolated
product indicated the structure of bicyclic ether 4a con-
taining a five-membered ether ring. Similarly, bicyclic
ether 4b was obtained from 3b. The results are shown in
Table 2. The solvent was investigated using a molar ratio
of 1,3-diol:iodine of 1:0.2, and a reaction time of 8 h. The
solvents used were acetonitrile (entry 1), toluene (entries 3
and 7), and hexane (entry 9). Similar to the reaction of 1a,
toluene was most suitable. When the temperature was
80℃, the yield of 4a was 89% (entry 7). When the reaction
mixture was refluxed, the yield decreased to 45% (entry 3).
The molar ratio of 1,3-diol:iodine was changed to 1:0.1
(entry 5), 1:0.2 (entry 7), and 1:0.5 (entry 8) and the most
suitable molar ratio was found to be 1:0.2. When the reac-
tion time was shor tened to 2 h (entr y 6), the yield
decreased to 67%. Thus, the most suitable conditions were
as follows: solvent, toluene; temperature, 80℃; time, 8 h;
and molar ratio of 1,3-diol:iodine, 1:0.2 (entry 8). However,
in the case of 3b, the most suitable solvent was hexane,
which differed from the reaction of 3a. Under similar con-
ditions of entry 9, 4b was obtained in 60% yield (entry 11).
The reaction of 1,3-diol 5a was performed using iodine
as a catalyst, and the spectroscopic data of the isolated
product suggested the structure of cyclic spiroether 6a,
containing a five-membered ether ring. The results are
shown in Table 3. Based on the results from the reactions
of 1 and 3, the reaction time was run for 8 h, and the molar
ratio of 1,3-diol:iodine was 1:0.2. The solvent was investi-
gated in the reaction of 5a. Acetonitrile (entry 1), toluene
(entries 2 and 3), and hexane (entry 4) were used of these
solvents, hexane was most suitable, providing a yield of
77%. Similar to 5a, the solvent was investigated in the
reaction of 5b (entries 5, 6, and 7). Hexane was also the
440
J. Oleo Sci. 57, (8) 437-443 (2008)
most suitable solvent and the yield of spiroether 6b was
68% (entry 7).
This method was applied to the etherification of ter-
penoic 1,3-diol, derived from (+)-camphor 7. The results
are summarized in Table 4. Due to the bulky structure, it
was hypothesized that iodination of 1,3-diol might occur
under severe reaction conditions. Therefore, the reaction
was performed under mild conditions in order to prevent
iodination: temperature, room temperature; reaction time,
3 h; and molar ratio of 1,3-diol:iodine, 1:0.2. The solvent
was investigated using acetonitrile (entry 3), toluene (entry
5), hexane (entry 6), and diethyl ether (entry 7). In these sol-
vents, acetonitrile was most efficient, and the yield was
high (91%) in spite of the mild conditions. The molar ratio
of 1,3-diol:iodine was changed from 0.01 to 0.5 (entries 1-4).
Although the molar ratio of iodine was a slight amount
(0.01), the reaction proceeded smoothly and the yield was
85% (entry 1).
A possible reaction mechanism is illustrated in Scheme
1. Hydrogen iodide, which is initially formed by the inter-
action of iodine with the hydroxyl group, acts as an acidic
catalyst to cause dehydration. An intermediate is formed
by skeleton rearrangement, and subsequent nucleophilic
attack by the oxygen atom on the carbocation results in the
formation of the five-membered ether ring. It is considered
that the other reactions proceeded in a similar mechanism.
The etherification of terpenoic 1,3-diol 9, derived from
(–)-fenchone 9, was investigated. The results are shown in
Table 5. At first, the reaction of 1,3-diol 9 was also carried
out under mild conditions, similar to that of 7: tempera-
ture, room temperature; reaction time, 3 h; and molar ratio
of 1,3-diol:iodine, 1:0.2. However, the reaction did not pro-
ceed well, giving a yield of only 9% (entry 1). Therefore, the
reaction was performed under reflux (entry 3). The yield
was greatly improved to 67%. Under these conditions, the
solvent was investigated (entries 3, 6, 7, and 8), and ace-
tonitrile and hexane were found to be efficient solvents.
When the reaction time was increased from 3 h to 8 h
(entry 4), the yield was slightly improved (74%). The reason
why the reaction of 1,3-diol 7 only proceeded smoothly at
room temperature is currently under investigation.
A comparison of the method using sulfuric acid1) with
the reaction using iodine was investigated in the reactions
of 1,3-diols 7 and 9. While the yield of the reaction of 7
using sulfuric acid was 80%, that using iodine was 91%.
However, the yield of the reaction of 9 using sulfuric acid
was 90%, while that using iodine was 74%. Thus, the reac-
tion using iodine compares favorably to the reaction using
sulfuric acid.
In conclusion, the etherification of 1,3-diols using iodine
as a catalyst proceeds smoothly to give the corresponding
five-membered ether rings. The yields obtained by this
method are as high as those obtained in the corresponding
reactions using acid catalysts.
 Synthesis of Five-membered Cyclic Ethers from 1,3-Diols

Table 2 The Intramolecular Cyclization of 1,3-Diols 3a,b.

Entry n Material Solvent I2 (eq.) Temp. (℃) time (h) Yield (%)
1 1 3a Acetonitrile 0.2 reflux 8 35
2 1 3a Toluene 0.1 reflux 8 53
3 1 3a Toluene 0.2 reflux 8 45
4 1 3a Toluene 0.5 reflux 8 52
5 1 3a Toluene 0.1 80 8 55
6 1 3a Toluene 0.2 80 2 67
7 1 3a Toluene 0.2 80 8 89
8 1 3a Toluene 0.5 80 8 63
9 1 3a Hexane 0.2 80 8 77
10 2 3b Acetonitrile 0.2 reflux 8 24
11 2 3b Hexane 0.2 reflux 8 60
12 2 3b Toluene 0.2 reflux 8 38
13 2 3b Toluene 0.2 reflux 8 45

Conditions: 1,3-diol, 2.5 mmol; solvent, 25 mL.

Table 3 The Intramolecular Cyclization of 1,3-Diols 5a,b.

Entry n Material Solvent Temp. (℃) Yield (%)
1 1 5a Acetonitrile reflux 9
2 1 5a Toluene reflux 38
3 1 5a Toluene 80 65
4 1 5a Hexane reflux 77
5 2 5b Acetonitrile reflux 3
6 2 5b Toluene 80 36
7 2 5b Hexane reflux 68

Conditions: 1,3-diol, 2.5 mmol; solvent, 25 mL; time, 8 h; molar ratio of 1,3-
diol:iodine, 1:0.2.

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J. Oleo Sci. 57, (8) 437-443 (2008)
 Y. Kasashima, H. Fujimoto, T. Mino et al.

Table 4 Iodine Catalyzed Intramolecular Etherification Table 5 Iodine Catalyzed Intramolecular Etherification
of 7. of 9.
Entry Solvent I2 (eq.) Yield (%) Entry Solvent I2 (eq.) Yield (%)

1 Acetonitrile 0.01 85 1a Acetonitrile 0.2 9

2 Acetonitrile 0.1 84 2 Acetonitrile 0.1 64
3 Acetonitrile 0.2 91 3 Acetonitrile 0.2 67
4 Acetonitrile 0.5 84 4b Acetonitrile 0.2 74
5 Toluene 0.2 48 5 Acetonitrile 0.5 60
6 Hexane 0.2 55 6 Toluene 0.2 24
7 Diethyl ether 0.2 11 7 Hexane 0.2 67
8 Diethyl ether 0.2 55
Conditions: 1,3-diol, 2.5 mmol; solvent, 25 mL; time 3 h; stirred
at room temperature. Conditions: 1,3-diol, 2.5 mmol; solvent, 25 mL; refluxed for 3 h.
a
Stirred at room temperature.
b
Refluxed for 8 h.

Scheme 1

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