Reactions of oxalyl chloride with 1,2-cycloalkanediols in the presence of triethylamine.

Article abstract of DOI:10.1248/cpb.50.83

The relationship between the product patterns and the configurations of 1,2-cycloheptane- and 1,2-cyclooctanediols 9 in the cyclocondensations with oxalyl chloride in the presence of triethylamine at 0 degrees C has been shown analogous to that obtained for 1,2-disubstituted acyclic ethylene glycols 1: cis-1,2-cyclooctanediol (9f) produced the cyclic oxalate 14f as the major product, while trans-1,2-cycloheptanediol (9e) and trans-1,2-cyclooctanediol (9g) formed the cyclic carbonates 12e, g as the major products. On the other hand, the cyclic oxalates 14a-d were formed as the major products from 1,2-cyclopentane- and 1,2-cyclohexanediols regardless of the configuration. These results can be accounted for by assuming the boat-like transition states for cyclizations of the half esters of comparatively rigid five- and six-membered diols 9a--d. The cyclic oxalates 14a, c may be directly formed through the resulting tetrahedral intermediates from cis-diols (9a,c), and the cyclic carbonates 12a,c as the minor products after ring inversion of the tetrahedral intermediates. The tetrahedral intermediates from the trans-isomers 9b, d cannot undergo ring inversion, producing no traces of the cyclic carbonates 12b, d.

Full text of DOI:10.1248/cpb.50.83

January 2002
Chem. Pharm. Bull. 50(1) 83—86 (2002)
83
Reactions of Oxalyl Chloride with 1,2-Cycloalkanediols in the Presence of
Triethylamine
b
Taisuke ITAYA,*,a Takehiko IIDA,a Itaru NATSUTANI,a and Masashi OHBA
Faculty of Pharmaceutical Sciencesa and Center for Instrumental Analysis,b Kanazawa University, Takara-machi,
Kanazawa 920–0934, Japan. Received August 15, 2001; accepted September 20, 2001
The relationship between the product patterns and the configurations of 1,2-cycloheptane- and 1,2-cyclooc-
tanediols 9 in the cyclocondensations with oxalyl chloride in the presence of triethylamine at 0 °C has been shown
analogous to that obtained for 1,2-disubstituted acyclic ethylene glycols 1: cis-1,2-cyclooctanediol (9f) produced
the cyclic oxalate 14f as the major product, while trans-1,2-cycloheptanediol (9e) and trans-1,2-cyclooctanediol
(9g) formed the cyclic carbonates 12e, g as the major products. On the other hand, the cyclic oxalates 14a—d
were formed as the major products from 1,2-cyclopentane- and 1,2-cyclohexanediols regardless of the configura-
tion. These results can be accounted for by assuming the boat-like transition states for cyclizations of the half es-
ters of comparatively rigid five- and six-membered diols 9a—d. The cyclic oxalates 14a, c may be directly formed
through the resulting tetrahedral intermediates from cis-diols (9a, c), and the cyclic carbonates 12a, c as the
minor products after ring inversion of the tetrahedral intermediates. The tetrahedral intermediates from the
trans-isomers 9b, d cannot undergo ring inversion, producing no traces of the cyclic carbonates 12b, d.
Key words 1,2-cycloalkanediol cyclocondensation; oxalyl chloride; cyclic oxalate ester; cyclic carbonate ester; stereocontrolled
cyclization; stereoelectronic effect
We have already reported that acyclic glycols 1 generally trans-1,2-cyclohexanediol (9d) should produce the carbonate
react with oxalyl chloride in tetrahydrofuran (THF) in the 12d exclusively, because it cannot undergo ring-inversion
presence of triethylamine at 0 °C or room temperature to and must go through the boat form 13 for the formation of
form the unstable cyclic oxalate 4 together with the cyclic the oxalate 14d. However, ‘normal’ cyclization of the s-trans
carbonates 2: unsubstituted, monosubstituted, and erythro- intermediate 10 leading to 11 (course A) suffers from severe
1,2-disubstituted ethylene glycols produced 4 and/or the steric congestion as depicted as 10A. In the case of the
polymeric oxalates as the major products, while threo-1,2- acyclic series, this steric interaction (5A) would be avoided
disubstituted ethylene glycols and pinacol afforded 2 as the by bringing the conformation close to the eclipsed form 5B.
major products.1)
If the cyclization of 10 takes place from the other side of the
According to our proposed mechanism1) illustrated in carbonyl plane as shown in 10B (course B), the tetrahedral
Chart 1, the formation of the carbonate 2a from pinacol (1a) intermediate 15 with a boat or twist-boat conformation is
in the presence of triethylamine is interpreted in terms of formed as a result of ‘abnormal’ cyclization. Once 15 is
stereochemically controlled formation of the tetrahedral in- formed, the exclusive formation of the cyclic oxalate 14d is
termediate 6 from the initially formed s-trans intermediate 5, expected through 16. Thus it is of considerable interest to
followed successively by deprotonation and stereoelectroni- study the reactions of 1,2-cycloalkanediols with oxalyl chlo-
cally controlled cleavage (the nonbonding electron pairs con- ride in the presence of triethylamine.
tributing to bond cleavage are shown as shaded lobes) of the
Table 1 summarizes the results of the reactions of some se-
C–C bond through 7 and 3. The cyclic oxalate 4a can be lected 1,2-cycloalkanediols with 1.1—1.3 mol eq of oxalyl
formed only after the conformer 7 changes into 8. The al- chloride in THF in the presence of triethylamine at 0 °C for
most exclusive formation of 2a from pinacol (1a) is attribut- 40 min. The formation of the cyclic oxalate 14b is suggestive
able to the large rotational barrier from 7 to 8 compared with of the absence of the ‘normal’ cyclization for trans-1,2-cy-
the activation energy for the decay of 7 leading to 3. If this is clopentanediol (9b). Unfortunately, the absence of the cyclic
the case, the corresponding tetrahedral intermediate 11 from carbonate 12b cannot be a proof against the ‘normal’ cy-
Chart 1
To whom correspondence should be addressed. e-mail: itaya@dbs.p.kanazawa-u.ac.jp
© 2002 Pharmaceutical Society of Japan

84
Vol. 50, No. 1
Chart 2
Table 1. Reactions of 1,2-Cycloalkanediols (9) with Oxalyl Chloride in
THF in the Presence of Triethylamine
Isolated yield
Estimated yield (%)a)
(%)
Substrate
14 12 Polymers
14 12
cis-1,2-Cyclopentanediol (9a)
trans-1,2-Cyclopentanediol (9b)b)
cis-1,2-Cyclohexanediol (9c)
trans-1,2-Cyclohexanediol (9d)
trans-1,2-Cycloheptanediol (9e)b)
cis-1,2-Cyclooctanediol (9f)
trans-1,2-Cyclooctanediol (9g)
75 18
44
86 Ͻ3
75
32 65
58 42
17 83
4
56
11
25
3
31 14
c)
0
—
0
60
64
—
0.5
0
51
0
c)
d)
—
0
26 37
c)
—
80
a) Determined by means of 1H-NMR spectroscopy. b) An excess (1.3 mol eq) of
oxalyl chloride was used. c) Could not be isolated. d) A trace if any.
Chart 3
Chart 4
clization because there is always a very limited possibility of diol (9g) afforded the cyclic carbonates 12e, g in 65 and 83%
the formation of the hitherto unknown highly strained 12b.2) yields, respectively. These results were anticipated because
1
However, the product ratio determined by H-NMR spec- the ‘normal’ cyclization is possible for the more flexible
troscopy for the reaction of trans-1,2-cyclohexanediol (9d) 9e, g, and the resulting intermediates (type 11) are not al-
shows that the cyclic oxalate 14d was formed in 75% yield lowed to undergo ring inversion. A closely related case to the
with no trace of the cyclic carbonate 12d, verifying that the reaction of 9e, g has been reported for 17 by Nicolaou et al.3)
‘normal’ cyclization is prohibited for 9d. On the contrary, without any comment on the mechanism of the formation of
trans-1,2-cycloheptanediol (9e) and trans-1,2-cyclooctane- the cyclic carbonate 18 as shown in Chart 3.

January 2002
85
that employed for the preparation of 12c. Recrystallization from hexane–
ether (2 : 1, v/v) afforded 12d as colorless prisms, mp 53—54.5 °C (lit.5) mp
53—54 °C). IR n Nmuajxol cmϪ1: 1792 (CϭO). 1H-NMR d: 1.31—1.52, 1.6—1.8,
1.84—2.03, 2.21—2.35 [2H each, m, (CH2)4], 4.02 (2H, m, two CH’s). 13C-
NMR d: 23.1, 28.2 (CH2), 83.5 (CH), 155.0 (CϭO).
cis-1,2-Cycloalkanediols 9a, c, f produced the oxalates 14
predominantly, analogous to the results obtained for acyclic
erythro-glycols.1) It is natural to consider that the reaction
with cis-1,2-cyclooctanediol (9f) proceeded in a manner sim-
ilar to that of the acyclic glycols. However, the cyclization
mode for the five- and six-membered ring cis-glycols 9a, c
must be the same as that for the trans isomers 9b, d. Accord-
ing to the hypothetical sequence exemplified for the reaction
of 9c in Chart 4, the oxalate 14c is directly formed from the
intermediate 21, and the carbonate 12c after a conforma-
tional change into 22 in contrast to the case of the acyclic
glycols (Chart 2).
In conclusion, we have reported that the relationship be-
tween the product patterns and the configurations of the
cyclic glycols 9 in the reactions with oxalyl chloride in the
presence of triethylamine is basically the same as that ob-
tained for 1,2-disubstituted acyclic ethylene glycols 1.1)
However, the five- and six-membered ring glycols 9b, d with
trans configuration are exceptions. Reactions of these com-
pounds presumably proceeded through boat-like transition
states, leading to the formation of the cyclic oxalates 14b, d
with a complete absence of the cyclic carbonates. Although
the five- and six-membered ring glycols 9a, c with cis config-
(؎)-trans-Hexahydro-4H-cyclohepta-1,3-dioxol-2-one (12e) A solu-
tion of triphosgene (223 mg, 0.751 mmol) in dichloromethane (5 ml) was
added to a solution of 9e6) (131 mg, 1.01 mmol) and pyridine (0.8 ml) in
dichloromethane (10 ml), and the mixture was stirred at 0 °C for 30 min. The
resulting solution was diluted with chloroform (5 ml), washed successively
with water, 5% aqueous citric acid, and saturated aqueous sodium bicarbon-
ate (5 ml each), dried over magnesium sulfate, and concentrated in vacuo to
leave a colorless oil. Flash chromatography [hexane–ethyl acetate (3 : 1,
v/v)] of this product afforded a colorless solid, which was recrystallized
from hexane–ethyl acetate (15 : 2, v/v), providing 12e (76 mg, 48%) as col-
Nujol
max
orless prisms, mp 79—79.5 °C (lit.4) mp 76—78 °C). IR n
cmϪ1: 1823
(CϭO). 1H-NMR d: 1.51 (2H), 1.69 (6H), 2.32 (2H) [m each, (CH2)5], 4.38
(2H, m, two CH’s); 13C-NMR d: 24.2, 24.4, 28.7 (CH2), 82.8 (CH), 154.9
(CϭO).
cis-Octahydrocycloocta-1,3-dioxol-2-one (12f)
A 2.0 M solution of
phosgene in toluene (1.7 ml, 3.4 mmol) was added to a solution of 9f
(433 mg, 3 mmol) and pyridine (1.10 ml, 13.6 mmol) in dry toluene (30 ml),
and the mixture was stirred at 0 °C for 1 h. Toluene (10 ml) was added to the
resulting mixture, and the whole was washed successively with water, 5%
aqueous citric acid, and saturated aqueous sodium bicarbonate (15 ml each),
dried over magnesium sulfate, and concentrated in vacuo, leaving crude 12f
(511 mg). This was recrystallized from hexane to give 12f (392 mg, 77%) as
colorless prisms, mp 101.5—102.5 °C (lit.7) mp 99—101 °C). MS m/z: 170
Nujol
uration are also considered to undergo cyclization through (Mϩ). IR n
cmϪ1: 1806 (CϭO). 1H-NMR d: 1.15—1.62 (6H), 1.63—
max
1.83 (2H), 1.92—2.15 (4H) [m each, (CH2)6], 4.70 (2H, m, two CH’s). 13C-
NMR d: 25.1, 25.9, 27.0 (CH2), 81.1 (CH), 154.1 (CϭO).
boat-like transition states, ring-inversion of the tetrahedral in-
termediates is possible in these cases, and the cyclic carbon-
ates 12a, c were formed as minor products.
(؎)-trans-Octahydrocycloocta-1,3-dioxol-2-one (12g) The diol 9g
(85% purity, 480 mg) was treated in a manner similar to that described for
the preparation of 12f, and the crude product that was obtained was purified
by flash chromatography [hexane–ethyl acetate (5 : 2, v/v)] to afford 12g
Experimental
General Notes All melting points were determined using a Yamato MP- (353 mg), mp 75—77 °C. This was recrystallized from hexane to give 12g as
1 or Büchi model 530 capillary melting point apparatus and values are cor- colorless prisms, mp 76.5—78.5 °C (lit.8) mp 79—81 °C). MS m/z: 170
Nujol
rected. Spectra reported herein were recorded on a JEOL JMS-SX102A (Mϩ). IR n
cmϪ1: 1796 (CϭO). 1H-NMR d: 1.14—1.35 (2H), 1.38—
max
mass spectrometer, a Hitachi model 320 UV spectrophotometer, a Shimadzu 1.60 (2H), 1.60—1.95 (6H), 2.26 (2H) [m each, (CH2)6], 4.54 (2H, m, two
FTIR-8100 or a FTIR-8400 IR spectrophotometer, a JEOL JNM-EX-270 or CH’s). 13C-NMR d: 22.0, 26.9, 33.3 (CH2), 82.9 (CH), 154.1 (CϭO).
a JEOL JNM-GSX-500 NMR spectrometer (measured in CDCl3 at 25 °C
Reactions of 1,2-Cycloalkanediols (9) with Oxalyl Chloride A solu-
with tetramethylsilane as an internal standard). Elemental analyses and MS tion of oxalyl chloride (1.1 mol eq) in THF (10 ml per mmol of 9) was added
measurements were performed by Dr. M. Takani and her associates at dropwise to a solution of 9 and triethylamine (5 mol eq) in THF (100 ml per
Kanazawa University. The following abbreviations are used: brϭbroad, mmol of 9) over a period of 30 min at 0 °C under nitrogen, and the mixture
mϭmultiplet.
was stirred at 0 °C for a further 10 min. The product ratios were determined
1
cis-Tetrahydro-4H-cyclopenta-1,3-dioxol-2-one (12a) A 2.0 M solu- by means of H-NMR spectroscopy on the basis of the relative areas of the
tion of phosgene in toluene (1.1 ml, 2.2 mmol) was added to a solution of 9a methine signals. The results are summarized in Table 1.
(204 mg, 2 mmol) and pyridine (0.71 ml, 8.8 mmol) in dry toluene (20 ml),
Reaction of cis-1,2-Cyclopentanediol (9a) Compound 9a (238 mg,
and the mixture was stirred at 0 °C for 15 min. The resulting mixture was di- 2.33 mmol), which had been dried over a mixture of molecular sieves 4A
luted with toluene (10 ml), washed successively with water, 5% aqueous cit- and 3A at 45 °C for 2 d, was treated with oxalyl chloride as described above.
ric acid, water, and saturated aqueous sodium bicarbonate (10 ml each). The The resulting mixture was found to contain cis-tetrahydro-5H-cyclopenta-
organic layer was dried over magnesium sulfate and concentrated in vacuo, 1,4-dioxin-2,3-dione (14a), 12a, the oxalate polymers, and 9a (75 : 18 : 4 : 4).
leaving a colorless oil (176 mg). The washings were combined, brought to It was concentrated to dryness in vacuo, and the residue was washed with
pH 5 by addition of 10% hydrochloric acid, saturated with sodium chloride, ether (50 and 20 ml). The combined washings were concentrated, and the
and extracted with benzene (3ϫ10 ml). The extracts were dried over magne- residue was submitted to Kugelrohr distillation. The distillate obtained
sium sulfate and concentrated in vacuo, leaving a colorless oil (47 mg). The below 170 °C and at 0.1—0.6 mmHg was purified by flash chromatography
crude products were combined and purified by flash chromatography [dichloromethane–ethyl acetate (15 : 1, v/v)], giving 12a (41 mg, 14%), mp
[hexane–ethyl acetate (3 : 2, v/v)] to give 12a as a colorless solid (174 mg, 29—30 °C, which was identical (by comparison of the IR spectra) with the
Nujol
68%), mp 29—29.5 °C (lit.4) mp 34—36 °C). MS m/z: 128 (Mϩ). IR n
authentic specimen prepared above. The distillate obtained at higher temper-
max
cmϪ1: 1800 (CϭO). 1H-NMR d: 1.57—1.90 (4H), 2.06—2.24 (2H) [m each, ature was dissolved in ether (20 ml), and the insoluble solid was removed by
(CH2)3], 5.11 (2H, m, two CH’s). 13C-NMR d: 21.5, 33.1 (CH2), 81.8 (CH), filtration. The ethereal solution was concentrated and the resulting solid was
155.4 (CϭO).
recrystallized from dry ether, giving 14a (113 mg, 31%), mp 75—76 °C.
cis-Hexahydro-1,3-benzodioxol-2-one (12c) A 2.0 M solution of phos-
Further recrystallization from ether afforded an analytical sample of 14a as
Nujol
gene in toluene (1.1 ml, 2.2 mmol) was added to a solution of 9c (232 mg, colorless prisms, mp 76.5—78 °C. MS m/z: 157 (Mϩϩ1). IR n
cmϪ1
:
max
2 mmol) and triethylamine (1.26 ml, 9 mmol) in dry THF (24 ml), and the 1771, 1755 (CϭO). 1H-NMR d: 1.79—1.90 (1H, m), 2.00—2.31 (5H, m)
mixture was stirred at 0 °C for 20 min. The resulting precipitate was filtered [(CH2)3], 4.99 (2H, m, two CH’s). 13C-NMR d: 19.3, 28.8 (CH2), 80.1 (CH),
off, and the filtrate was concentrated in vacuo. The residue was purified by 151.9 (CϭO). Anal. Calcd for C7H8O4: C, 53.85; H, 5.16. Found: C, 53.76;
flash chromatography [hexane–ethyl acetate (3 : 2, v/v)] to give 12c as a
H, 5.21. This sample was found to be decomposed after storage at Ϫ20 °C
for two months.
Reaction of (؎)-trans-1,2-Cyclopentanediol (9b) The reaction mix-
ture was filtered, and the filtrate was concentrated in vacuo, leaving a brown
oil. This was found to be composed of (Ϯ)-trans-tetrahydro-5H-cyclopenta-
Nujol
semi-solid (110 mg, 39%) (lit.5) mp 38—39 °C). IR n
cmϪ1: 1775
max
(CϭO). 1H-NMR d: 1.35—1.53 (2H), 1.55—1.72 (2H), 1.82—1.95 (4H) [m
each, (CH2)4], 4.68 (2H, m, two CH’s). 13C-NMR d: 19.1, 26.7 (CH2), 75.7
(CH), 155.3 (CϭO).
(؎)-trans-Hexahydro-1,3-benzodioxol-2-one (12d) This compound 1,4-dioxin-2,3-dione (14b) [d 4.71 (m)] and the oxalate polymers [d 5.27
was obtained in 69% yield from 9d (349 mg, 3 mmol) in a manner similar to (m)]. This material was unstable to purification.

86
Vol. 50, No. 1
Reaction of cis-1,2-Cyclohexanediol (9c) The reaction mixture ob- ings were concentrated to dryness in vacuo to give a mixture of cis-octahy-
tained from 9c (232 mg, 2 mmol) was filtered, and the insoluble solid was drocycloocta-1,4-dioxin-2,3-dione (14f) and 12f. The residue was triturated
washed with THF (40 ml). The combined filtrate and washings were concen- with ether (15 ml), and the insoluble solid was removed by filtration. The
trated to dryness in vacuo. The resulting mixture of cis-hexahydro-1,4-ben- ethereal solution was kept in a refrigerator overnight, and the precipitate that
zodioxin-2,3-dione (14c), 12c, and the oxalate polymers was submitted to separated was collected by filtration, giving crude 14f (102 mg, 26%), mp
Kugelrohr distillation. The forerun (30 mg) was applied to flash chromatog- 72.5—75 °C. On the other hand, the solid that remained undissolved in ether
raphy [hexane–ethyl acetate (3 : 2, v/v)] to afford 12c (1.3 mg, 0.5%) as a
at room temperature was extracted with boiling ether (2ϫ10 ml), and the ex-
1
colorless oil, which was identical (by comparison of the H-NMR spectra) tracts were combined with the mother liquor from which crude 14f was ob-
with an authentic specimen. The distillate (231 mg) obtained at 140—200 °C tained. The mixture was concentrated and applied to flash chromatography
and 0.8 mmHg was dissolved in hot ether. The insoluble solid was removed [hexane–ethyl acetate (3 : 1, v/v)], giving 12f (126 mg, 37%), mp 98.5—
by filtration. The ethereal solution was concentrated to afford crude 14c 99.5 °C, which was identical (by comparison of the IR spectra) with an au-
(204 mg, 60%), mp 81.5—83 °C. Recrystallization of this product from car- thentic specimen. Recrystallization of crude 14f from carbon tetrachloride
bon tetrachloride afforded an analytical sample of 14c as colorless prisms, afforded an analytical sample as colorless prisms, mp 76—77 °C. MS m/z:
Nujol
max
ϩ
Nujol
cmϪ1: 1761, 1748
max
mp 84—85 °C (lit.9) mp 84—84.5 °C). MS m/z: 171 (Mϩϩ1). IR n
199 (M ϩ1). UV l
nm (e): 273 (56). IR n
CH3CN
max
cmϪ1: 1771, 1755 (CϭO). 1H-NMR d: 1.52 (2H, m), 1.77 (2H, m), 1.97
(CϭO); n
cmϪ1: 1782, 1763 (CϭO). 1H-NMR d: 1.55 (2H), 1.65 (4H),
CHCl3
max
(4H, br) [(CH2)4], 4.80 (2H, br, two CH’s). 13C-NMR d: 21.0, 28.5 (CH2), 1.81 (2H), 2.03 (2H), 2.16 (2H) [m each, (CH2)6], 4.89 (2H, m, two CH’s).
76.7 (CH), 153.3 (CϭO). Anal. Calcd for C8H10O4: C, 56.47; H, 5.92. 13C-NMR d: 22.5, 25.3, 27.4 (CH2), 79.6 (CH), 153.2 (CϭO). Anal. Calcd
Found: C, 56.28; H, 5.95.
for C10H14O4: C, 60.60; H, 7.12. Found: C, 60.55; H, 7.02.
Reaction of (؎)-trans-1,2-Cyclohexanediol (9d) The precipitate that
Reaction of (؎)-trans-1,2-Cyclooctanediol (9g) The precipitate was
separated from the reaction mixture obtained from 9d (349 mg, 3 mmol) was removed from the reaction mixture obtained from 9g (288 mg, 2 mmol) by
removed by filtration and washed with THF (30 ml). The combined filtrate filtration and washed with THF (30 ml). The combined filtrate and washings
and washings were concentrated to dryness in vacuo to give a mixture of were concentrated to dryness in vacuo to provide a mixture of (Ϯ)-trans-oc-
(Ϯ)-trans-hexahydro-1,4-benzodioxin-2,3-dione (14d) and the oxalate poly- tahydrocycloocta-1,4-dioxin-2,3-dione (14g) and 12g. Flash chromatography
mers. This was submitted to Kugelrohr distillation. The distillate (667 mg) [hexane–ethyl acetate (5 : 2, v/v)] of this product gave 12g (272 mg, 80%),
obtained at 170—200 °C and 0.8—0.9 mmHg was dissolved in hot ether. mp 69—72 °C, which was identical (by comparison of the IR spectra) with
The insoluble solid was removed by filtration. The ethereal solution was an authentic specimen.
concentrated to afford crude 14d (328 mg, 64%), mp 102—103.5 °C. Re-
crystallization of this product from toluene afforded an analytical sample of References and Notes
14d as colorless prisms, mp 110—113 °C (lit.9) mp 111—112 °C). MS m/z:
1) a) Itaya T., Iida T., Eguchi H., Chem. Pharm. Bull., 41, 408—410
(1993); b) Iida T., Itaya T., Tetrahedron, 49, 10511—10530 (1993).
2) No trace of 12b was formed in the reaction of 9b with an excess of
triphosgene in dichloromethane in the presence of pyridine at room
temperature for 9 h.
3) Nicolaou K. C., Sorensen E. J., Discordia R., Hwang C.-K., Minto R.
E., Bharucha K. N., Bergman R. G., Angew. Chem. Int. Ed. Engl., 31,
1044—1046 (1992).
4) Kruper W. J., Dellar D. V., J. Org. Chem., 60, 725—727 (1995).
5) Kardouche N. G., Owen L. N., J. Chem. Soc., Perkin Trans. 1, 1975,
754—761.
6) Hayashi M., Terashima S., Koga K., Tetrahedron, 37, 2797—2803
(1981).
ϩ
Nujol
cmϪ1: 1786, 1759
max
CH3CN
max
171 (M ϩ1). UV l
nm (e): 269 (56). IR n
1
CHCl3
(CϭO); n
cmϪ1: 1782 (CϭO). H-NMR d: 1.37, 1.58. 1.91, 2.30 [2H
max
each, m, (CH2)4], 4.45 (2H, m, two CH’s). 13C-NMR d: 22.7, 29.2 (CH2),
80.0 (CH), 153.6 (CϭO). Anal. Calcd for C8H10O4: C, 56.47; H, 5.92.
Found: C, 56.61; H, 5.84.
Reaction of (؎)-trans-1,2-Cycloheptanediol (9e) The insoluble solid
that separated from the reaction mixture obtained from 9e6) (260 mg,
2 mmol) was removed by filtration, and the filtrate was concentrated to dry-
ness in vacuo to give a mixture of (Ϯ)-trans-hexahydro-5H-cyclohepta-1,4-
dioxin-2,3-dione (14e), 12e, and the oxalate polymers. The mixture was sub-
mitted to flash chromatography [hexane–ethyl acetate (3 : 1, v/v)] to afford
crude 12e (159 mg, 51%). Recrystallization of this sample from
hexane–ethyl acetate (5 : 1, v/v) afforded 12e, mp 79—79.5 °C, which was
7) Murthy K. S. K., Dhar D. N., J. Heterocycl. Chem., 21, 1721—1725
(1984).
1
identical (by comparison of the IR and H-NMR spectra) with an authentic
sample.
8) Semmelhack M. F., Stauffer R. D., Tetrahedron Lett., 1973, 2667—
2670.
9) Lloyd W. D., Navarette B. J., Shaw M. F., Org. Prep. Proced. Int., 7,
207—210 (1975).
Reaction of cis-1,2-Cyclooctanediol (9f) The precipitate that separated
from the reaction mixture obtained from 9f (288 mg, 2 mmol) was removed
by filtration and washed with THF (50 ml). The combined filtrate and wash-