Heteromacrocycles from Ring-Closing Metathesis of Unsaturated Furanic Ethers

Article abstract of DOI:10.1081/SCC-120026858

New 2,5-bix(unsaturated alkyloxymethyl)-furan led to macrocyclic furanic derivatives in the presence of Grubb's catalyst via dimerization or direct intramolecular metathesis according to the length of the sidearm.

Full text of DOI:10.1081/SCC-120026858

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Heteromacrocycles from Ring-Closing Metathesis of
Unsaturated Furanic Ethers
Louis Cottier a , Gérard Descotes a & Yaya Soro a
a Université Claude-Bernard Lyon I, Laboratoire de Chimie Organique II, UMR CNRS-
Université N° 5622, ESCPE-Lyon, Villeurbanne, France
Published online: 21 Aug 2006.
To cite this article: Louis Cottier , Gérard Descotes & Yaya Soro (2003): Heteromacrocycles from Ring-Closing Metathesis
of Unsaturated Furanic Ethers, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 33:24, 4285-4295
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 24, pp. 4285–4295, 2003
Heteromacrocycles from Ring-Closing
Metathesis of Unsaturated Furanic Ethers
*
Louis Cottier, Gerard Descotes, and Yaya Soro
´
Universite
Laboratoire de Chimie Organique II,
UMR CNRS-Universite
Nꢀ 5622, ESCPE-Lyon,
´
Claude-Bernard Lyon I,
´
Villeurbanne, France
ABSTRACT
New 2,5-bis(unsaturated alkyloxymethyl)-furan led to macrocyclic
furanic derivatives in the presence of Grubb’s catalyst via dimeri-
zation or direct intramolecular metathesis according to the length
of the sidearm.
Key Words: Oxygen heterocycles; Ring-closing metathesis; Macro-
cycles.
*Correspondence: Louis Cottier,
Laboratoire de Chimie Organique II, UMR CNRS-Universite
Universite
´
Claude-Bernard
Lyon
I,
´
Nꢀ 5622,
ESCPE-Lyon, Bat. 308, 43, Blvd. du 11 Novembre 1918, 69622 Villeurbanne,
France; Fax: (33)4 72 44 81 60; E-mail: louis.cottier@univ-lyon1.fr.
4285
DOI: 10.1081/SCC-120026858
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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4286
Cottier, Descotes, and Soro
INTRODUCTION
As part of project to develop the use of the 5-hydroxymethylfurfural
(HMF)[1] 1, issued from the acid catalyzed dehydration of fructose
or inulin,[2] we thought to transform the HMF 1 to unsaturated
macrocycle polyether compounds containing furan subcyclic unit. Such
heteromacrocycles with a number of structure limited due to the
presence of carbon–carbon double bonds should presented complexation
properties[3] and alkali metal cation–p interactions.[4] These heteromacro-
cyclic substrates could be easily prepared from unsaturated molecules via
the ring closing metathesis (RCM) catalyzed by carbene transition
complexes (Mo, Ru).[5] The cyclization of allylic ethers or unsaturated
amines to the corresponding five, six or seven membered oxa or azacycles
has been demonstrated.[5b,5d,6] Very recently Tae and Yang[7] described
the olefin metathesis macrocyclization of p-bis[(allyl or 4-penten-1-yloxy)
methyl]benzene leading to mono, di, or trimeric products.
In this article we report the syntheses of heteromacrocycles 6 and 9
via the ring closing metathesis (RCM) of 2,5-disubstituted furans 3a
and 3b catalyzed by commercially available Grubbs’ catalyst.[5b,6b]
Until now, some publications mentioned the metathesis of compounds
containing furanic moiety using tungsten alkylidene complexe,[8] molyb-
denum,[9] or ruthenium[10] catalysts but nobody applied RCM to
2,5-unsaturated disubstituted furans. We used the benzylidene-bis
(tricyclohexylphosphine) ruthenium dichloride 4 (Grubbs’ catalyst)
because of its good properties (high reactivity, stability to air and various
solvent, remarkable functional group tolerance).
RESULTS AND DISCUSSION
The 2,5-unsaturated disubstituted furans 3a and 3b were prepared
according to the Williamson reaction between the 2,5-bis (hydroxy-
methyl)-furan 2 issued from hydroxymethylfurfural (HMF)[1b] 1 and
the appropriate bromide. The best yield in 3a was obtained using
sodium hydride in presence of tetrabutylammonium iodide (TBAI) and
a mixture of THF and DMSO as solvent. The bis ether 3b was
prepared in 71% yield as described for 2a. This yield was increased up
to 95% under liquid liquid phase transfer. Unfortunately we were not
able to obtain the butenyl ether from 2 and the 4-bromobut-1-ene
because, in the basic conditions, a,b-elimination reaction yielding
butadiene competes with the slower substitution reaction. It must be

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Unsaturated Furanic Ethers
4287
Scheme 1.
noticed that Tae and Yang[7]did not prepare the p-bis[(3-buten-1-yloxy)-
methyl]benzene but the lower or upper homologues. (Sch. 1)
The ring closure of furanic compounds 3 in presence of benzylidene
ruthenium complex 4 was realized under high dilution to avoid an easy
cross metathesis polymerization which occurred with a concentration less
than 0.04 mol/L. The observed results of different attempts are summa-
rized in the Table 1. The formation of 6 (ZZ and EE) instead of 5 is
probably due to the conformational constraints in the original substrate

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4288
Cottier, Descotes, and Soro
Table 1. Ring-closing metathesis of compounds 3a and 3b with Grubbs’
catalyst 4.
Substratea
(amount in mmol)
Catalyst 5
mol%
Products
(Yield [%])
Time (h)
Isomers, [%]
3a (1)b
3a (1)c
2.5
2.5
2.5
10
18
18
4.5
18
4
6 (26)
6 (63)
6 (48)
6 (51)
9 (96)
ZZ/EE, 70/30
ZZ/EE, 74/26
ZZ/EE, 78/22
ZZ/EE, 70/30
Z/E, 61/39e
3a (1)c,d
3a (1)c
3b (0.5)c
10
aIn dichloromethane at reflux.
bConcentration in mol/L:0.02.
cConcentration in mol/L:0.005.
dUnder sonication.
eThe ratio could be inverted.
Scheme 2.
and in the eventual product 5. The activation with ultrasound did not
increase the rate or the yield.
It must be pointed out that De Armas et al.[10b] did not observe such
a dimerization during the ring closing metathesis of 7-(4-pentenyl)-L-
arabino-hept-1-enitol derivative A. They reported the formation of a
medium sized bridged oxabicyclo[6.2.1] alkene B while Tae and Yang[7]
described the formation of a dimeric substrate from the p-bis[(allyloxy)-
methyl]benzene with the same catalyst 4. (Sch. 2)
The structure of macrocycles 6 was established according to the
mass spectra data because the NMR spectra could agreed with a bicyclic
compound 5 or a bis furanic macrocycle 6. Fortunately, the FAB mass
spectra showed a molecular ion peak at m/z equal to 361 [M þ H]þ or to
383 [M þ Na]þ proving the dimeric structure of 6. Due to the presence of,
1
at least, a plane of symmetry, the H and 13C NMR spectra, showed
only one signal for each of protons 4-H, 6-H, 7-H and 8-H and for

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Unsaturated Furanic Ethers
4289
Scheme 3.
each of carbons C-4, C-5, C-6, C-7, and C-8. An attempt to obtain the
compound 5 with the configuration Z from the chloro alcohol 8 (Sch. 3)
did not give the compound 5 but led to the macrocycle 6. This result
allows to specify the stereochemistry Z, Z and E, E of the obtained
isomers 6. The restricted number of the signals in 13C NMR excluded
the formation of the Z,E stereoisomer (Sch. 3).
In the case of the furanic ether 3b with longer sidechains, the RCM
gave the monomeric bicyclic compound 9 with an excellent yield (96%) as
a mixture of stereoisomers Z/E in a ratio 3/2 or 2/3. The bicyclic structure
was established according to NMR and mass spectra. As the compounds
9 have elements of symmetry, the configuration Z or E of each isomer
could not be attributed from NMR. Unfortunately we have not be able
to get a single crystal of the major isomer 9, which is solid, to establish
the structure with an X-ray analysis
CONCLUSION
The HMF, issued from the acid catalyzed dehydration of fructose or
inulin, can easily lead to 2,5-unsaturated diethers via the 2,5- bis(hydroxy-
methyl)-furan. The RCM reaction of these ethers were carried out in
presence of commercial and stable Grubbs’ catalyst with good yields.
The structure of the macrocyclic unsaturated polyethers depends on the
length of the sidearms. If, on both sidearms, there are three atoms
between the carbon–carbon double bond and the furan moiety, a
cyclodimerization was observed leading to a heteromacrocycle with two

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4290
Cottier, Descotes, and Soro
furan subcyclic units. The allylic ether 3a underwent probably a cross
metathesis followed by a RCM leading to the macrocycle 6 and not to the
monofuranic compound 5. But if the sidearms are longer, an unsaturated
macrocyclic polyether containing one furan subcyclic unit was achieved.
The bis pentenyl ether 3b gave the bicyclic product 9 through a direct
intramolecular metathesis. These syntheses could be applied to make
larger unsaturated heteromacrocycles.
EXPERIMENTAL SECTION
General Remarks. Melting point were uncorrected. Proton NMR
spectra[11] at 200 MHz and 13C NMR spectra[11] at 50 MHz were recorded
by using a Bruker spectrometer AC 200. Mass spectra were measured
with a Finnigan MAT 95 XL spectrometer. Column chromatography
was performed using Geduran Si 60 silica gel (E. Merck). The ratios of
solvents were measured in volume. Grubb’s catalyst 4 was purchased
from Aldrich.
2,5-bis-Hydroxymethyl-furan (2). To 5-hydroxymethylfurfural
(12.3 g, 97.5 mmol) dissolved in dry methanol (100 mL) and maintained
at 4ꢀC was added slowly sodium borohydride (7.5 g, 198.3 mmol). The
reaction was stirred at room temperature for 15 min. Then the methanol
was evaporated under vacuum and water was added to the residue. This
new mixture was neutralized by addition of HCl (2N) and then extracted
with ethyl acetate (7 ꢁ 40 mL). The organic phase was dried (MgSO4) and
concentrated. The raw product was chromatographed (dichloromethane/
ethyl acetate, 10:1) to give 2 (12.1 g, 97%). White solid. Rf ¼ 0.38
(dichloromethane/ethyl acetate, 10:1). M.p.: 75ꢀC. Lit.[12] M.p. 74–75ꢀC;
1H and 13C NMR data were in agreement with those reported in the
literature;[12] 1H NMR (200 MHz, [d6] DMSO): ꢀ ¼ 6.2 (s, 1H, 3-H), 5.1
(t, 1H, OH), 4.3 (d, 2H, J6a,6b ¼ 5.6, 6-Ha, 6-Hb). 13C NMR (50 MHz, [d6]
DMSO): ꢀ ¼ 154.8 (C-2), 107.6 (C-3), 55.9 (C-6).
2,5-bis-Allyloxymethyl-furan (3a). Into a suspension of HNa (0.2 g,
8.3 mmol) in THF (4 mL) was dropped a solution of 2 (0.32 g, 2.5 mmol)
in dry DMSO (2 mL). The mixture was stirred at room temperature for
30 min and then was heated at 40ꢀC before adding tetrabutylammonium
iodide (0.15 g, 0.4 mmol) and allyl bromide (1.2 g, 10 mmol). The reaction
was monitored by TLC (petroleum ether/ethyl acetate, 1:1). The reaction
was stirred for 18 h until the alcohol 2 had been converted. Then diethyl
ether (4 mL) and water (5 mL) were added and the solution was extracted
with diethyl ether (5 ꢁ 15 mL). The combined organic layers were dried
(MgSO4) and concentrated. The crude product was chromatographed

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Unsaturated Furanic Ethers
4291
(petroleum ether/ethyl acetate, 5/1 200 mL and then 1/1) to give 3a (0.4 g,
77%). Colorless oil. Rf ¼ 0.38 (petroleum ether/ethyl acetate,
5/1); 1H NMR (200 MHz, CDCl3): ꢀ ¼ 6.23 (s, 2H, 4-H), 5.92 (ddt,
2H, J8,7 ¼ 5.6 Hz, J8,9b ¼ 10.3 Hz, J8,9a ¼ 17.2 Hz, 8-H), 5.27 (dq, 2H,
J9a,7 ¼ J9a, J9b ¼ 1.5 Hz, J9a,8 ¼ 17.2 Hz, 9a-H), 5.24 (dq, 2H,
J9b,9a ¼ J9b,7 ¼ 1.5 Hz, J9b,8 ¼ 10.3 Hz, 9b-H), 4.44 (s, 4H, 6-H), 4.03 (dt,
4H, J7,9b ¼ J7,9a ¼ 1.5 Hz, J7,8 ¼ 5.6 Hz, 7-H). 13C NMR (50 MHz,
CDCl3): ꢀ ¼ 152.1 (C-5), 134.5 (C-8), 117.5 (C-9), 110.0 (C-4), 71.0
(C-7), 64.0 (C-6); MS (CI isobutane) C12H16O3 (M:208): m/z ¼ 209
[M þ H]þ. Anal. calcd. for C12H16O3: C, 69.20; H, 7.74. Found:
C, 68.87; H, 7.66.
2,5-bis-Pent-4-enyloxymethyl-furan (3b). The compound 3b was
obtained according to the same procedure with a yield of 71% but the
following procedure gave a better yield—A mixture of diol 2 (130 mg,
1 mmol), 5-bromo-1-pentene (447 mg, 3 mmol), aliquat 336 (81 mg,
0.2 mmol) and KOH (9.4 N, 0.3 mL) was stirred at 85ꢀC. The reaction
was monitored by TLC (petroleum ether/ethyl acetate, 5:1). After 24 h,
the reaction mixture was filtered and concentrated. The residue was
chromatographed (petroleum ether/ethyl acetate, 5:1) to give 3b
(251 mg, 0.95 mmol, 95%). Light yellow oil. Rf ¼ 0.46 (petroleum ether/-
1
ethyl acetate); H NMR (200 MHz, CDCl3): ꢀ ¼ 6.26 (s, 2H, 4-H), 5.81
(m, 2H, J10,9 ¼ 6.6 Hz, J10,11b ¼ 10.2 Hz, J10,11a ¼ 17 Hz, J10,8 ¼ 6.7 Hz, 10-
H), 5.05 (dq, 2H, J11a,11b ¼ 1.9 Hz, J11a,10 ¼ 17 Hz, J11a,9 ¼ 1.2 Hz, 11a-H),
4.94 (dq, 2H, J11b,11a ¼ 1.9 Hz, J11b,10 ¼ 10.2 Hz, J11b,9 ¼ 1 Hz, 11b-H),
4.43 (s, 4H, 6-H), 3.49 (t, 4H, J7,8 ¼ 6.6 Hz, 7-H), 2.11 (m, 4H,
J8,77 ¼ 6.6 Hz, J8,9 ¼ 6.8 Hz, J8,10 ¼ 7 Hz, 8-H), 1.7 (m, 4H, J9,8 ¼ 6.8Hz,
J9,10 ¼ 6.6 Hz, J9,11 Hz ¼ 1 Hz, J9,11a ¼ 1.2 Hz, 9-H); 13C NMR (50 MHz,
CDCl3): ꢀ ¼ 152.3 (C-5), 138.2 (C-10), 114.8 (C-11), 109.7 (C-3), 69.6
(C-7), 64.9 (C-6), 30.3 (C-8), 28.8 (C-9); MS (CI isobutane) C16H24O3
(M:264): m/z ¼ 265 [M þ H]þ. Anal. calcd. for C16H24O3: C, 72.69;
H, 9.15. Found: C, 72.51; H, 9.04.
3,8,15,20,25,26-Hexaoxa-Tricyclo[20.2.1.110,13] hexacosa-1(24),5,10,
12,17,22-hexaene (6 ZZ and EE). A. from allyloxymethyl-furan 3a.—A
solution of Grubbs’ catalyst 4 (20.6 mg, 0.025 mmol) in dry and degassed
dichloromethane (20 mL) was added by syringe into a flask containing
the furanic compound 3a (208 mg, 1 mmol) dissolved in dry and degassed
dichloromethane (180 mL). The mixture, heated at 40ꢀC, was stirred for
18 h. The reaction was monitored by TLC (dichloromethane/acetone,
5:0.2). The reaction mixture was concentrated. The residue was chroma-
tographed (dichloromethane/acetone, 5:0.2) to give
6
(227 mg,
0.63 mmol) as a mixture of diastereoisomers. Each isomer was separated
with a second chromatography (petroleum ether/ethyl acetate, 1:2) giving

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Cottier, Descotes, and Soro
the isomer 6 ZZ (148 mg, 46.6%) and the isomer 6 EE (59 mg, 16.4%);
the ratio of the stereoisomers ZZ/EE was equal to 74/26.
B. from chloro-alcohol 8.—Into a suspension of HNa (10 mg,
0.4 mmol) and TBAI (12 mg, 0.03 mmmol) in THF (2.5 mL) was dropped
a solution of 8 (40 mg, 0.2 mmol) in dry DMSO (1.5 mL). The mixture
was stirred at room temperature for 24 h. After the work-up such as 3a,
the crude product was chromatographed (petroleum ether/ethyl acetate,
1:2) to give 6 ZZ (26 mg, 0.07 mmol, 72%).
Compound 6 (5Z, 17Z). White powder. Rf ¼ 0.66 (petroleum ether/
ethyl acetate, 1:2). M.p.: 92ꢀC. H NMR (200 MHz, CDCl3): ꢀ ¼ 6.26 (s,
1
4H, 4-H), 5.74 (t, 4H, J8,7a ¼ J8,7b ¼ 4.9 Hz, 8-H), 4.41 (s, 8H, 6-H), 4.06
(t, 8H, J7a,8 ¼ J7b,8 ¼ 4.9 Hz, 7-H). 13C NMR (50 MHz, CDCl3): ꢀ ¼ 152.3
(C-5), 129.6 (C-8), 110.0 (C-4), 69.6 (C-7), 63.7 (C-6). HRMS calcd. for
C20H25O6 [M þ H]þ: 361.1651. Found: 361.1648.
Compound 6 (5E, 17E). White powder. Rf ¼ 0.77 (petroleum ether/
ethyl acetate, 1:2). M.p.: 89–90ꢀC. H NMR (200 MHz, CDCl3): ꢀ ¼ 6.26
1
(s, 4H, 4-H), 5.82 (dd, 4H, J8,7a ¼ 1.3 Hz, J8,7b ¼ 2.9Hz, 8-H), 4.44 (s, 8H,
6-H), 4.01 (d, 4H, J7a,8 ¼ 1.3 Hz, 7a-H), 4.02 (d, 4H, J7b–8 ¼ 2.9 Hz,
7b-H). 13C NMR (50 MHz, CDCl3): ꢀ ¼ 152.1 (C-5), 129.8 (C-8), 110.3
(C-4), 64.7 (C-7), 63.7 (C-6). HRMS calcd. for C20H25O6 [M þ H]þ:
361.1651. Found: 361.1649.
(2Z)-5-(4-Chlorobut-2-enyloxymethyl-furan)-2-carbaldehyde (7). Into
a suspension of HNa (190 mg, 7.9 mmol) in THF (8 mL) was added the
hydroxymethylfurfural
1
(500 mg, 3.96 mmol), (2Z)-1,4-dichloro-
but-2-ene (4.1 mL, 39 mmol) and TBAI (235 mg). The mixture was
heated at 40ꢀC for 24 h. The reaction mixture was concentrated and
chromatographed (petroleum ether/ethyl acetate, 2:3) to give 7 (132 mg,
1
13%). Yellow oil. Rf ¼ 0.8 (petroleum ether/ethyl acetate, 2:3). H NMR
(200 MHz, CDCl3): ꢀ ¼ 9.63 (s, 1H, CHO), 7.23 (d, 1H, J3,4 ¼ 3.55 Hz,
3-H), 6.56 (d, 1H, J4,3 ¼ 3.55 Hz, 4-H), 5.77 (m, 2H, 8-H and 9-H), 4.44
(s, 2H, 6-H), 4.12 (m, 4H, 7-H and 10-H). 13C NMR (50 MHz, CDCl3):
ꢀ ¼ 177.7 (CHO), 158.0 (C-5), 157.7 (C-2), 129.9 (C-9), 129.1 (C-8), 122.0
(C-3), 111.5 (C-4), 65.7 (C-7), 64.2 (C-6), 39.0 (C-10). HRMS calcd. for
C10H12O3Cl [M þ H]þ: 215.0475. Found: 215.0476.
(2Z)-[5-(4-Chlorobut-2-enyloxymethyl)-furan-2-yl]-methanol (8). The
compound 8 was obtained according to the procedure of compound 1.
The aldehyde 7 (100 mg, 0.46 mmol) with NaBH4 (35 mg, 0.9 mmol in dry
methanol (4 mL) gave after usual work-up and chromatography (petro-
leum ether/ethyl acetate, 2:3) the alcohol 8 (45.7 mg, 0.21 mmol, 46%).
Colorless oil. Rf ¼ 0.35 (petroleum ether/ethyl acetate, 2:3). 1H NMR
(200 MHz, CDCl3): ꢀ ¼ 6.3 (d, 1H, J3,4 ¼ 3.2 Hz, 3-H), 6.25 (d, 1H,
J4,3 ¼ 3.2 Hz, 4-H), 5.77 (m, 2H, 8-H and 9-H), 4.59 (s, 2H, 11-H), 4.44

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Unsaturated Furanic Ethers
4293
(s, 2H, 6-H), 4.12 (m, 4H, 7-H and 10-H). 13C NMR (50 MHz, CDCl3):
ꢀ ¼ 154.8 (C-5), 151.2 (C-2), 130.3 (C-9), 128.8 (C-8), 110.5 (C-3), 108.4
(C-4), 64.9 (C-7), 64.1 (C-6), 57.3 (C-11), 39.1 (C-10). HRMS
C10H13O3Cl [M]þ: 216.0553. Found: 216.0550.
3,8,15,20,25,26-Hexaoxa-tricyclo[20.2.1.110, 13] hexacosa-1(24),5,10,12,
17,22-hexaene (9 Z/E or E/Z). A solution of Grubb’s catalyst 4 (41 mg,
0.05mmol) in dry and degassed dichloromethane (10 mL) was added by
syringe into a flask containing 3b (132mg, 0.5 mmol) dissolved into
dichloromethane (90mL). The mixture, heated at 40ꢀC, was stirred for
4 h. Then the solvent was evaporated and the residue was chromato-
graphed (petroleum ether/ethyl acetate, 1:1) to give
9 (113mg,
0.48mmol, 96%) as a mixture of isomers in a ratio 61/39. These isomers
were separated with a second chromatography (petroleum ether/ethyl
acetate, 5:0.5) providing a minor product (44 mg, 0.18mmol) and a
major product (69 mg, 0.29mmol)
Minor product 9. Colorless oil. Rf ¼ 0.23 (petroleum ether/ethyl
1
acetate, 5:0.5). H NMR (200 MHz, CDCl3): ꢀ ¼ 6.23 (s, 2H, 4-H), 5.19
(dd, 2H, J10,9a ¼ 4.4 Hz, J10,9b ¼ 5.3 Hz, 10-H), 4.44 (s, 4H, 6-H), 3.41 (t,
4H, J7a,8a ¼ J7a,8b ¼ J7b,8a ¼ J7b,8b ¼ 7.2 Hz, 7-H), 2.02 (m, 4H, 8-H), 1.53
(m, 4H, 9-H). 13C NMR (50 MHz, CDCl3): ꢀ ¼ 153.1 (C-5), 129.1 (C-10),
110.2 (C-4), 68.(C-7), 64.3 (C-6), 28.1 (C-8), 27.9 (C-9). MS C14H20O3
(M:236): m/z ¼ 236 [M]þ.
Major product 9. White powder. Rf ¼ 0.26 (petroleum ether/ethyl acet-
ate, 5:0.5). M.p.: 37ꢀC. 1H NMR (200 MHz, CDCl3): ꢀ ¼ 6.29 (s, 2H, 4-H),
5.24 (dd, 2H, J10,9a ¼ 2.2 Hz, J10,9b ¼ 5.3 Hz, 10-H), 4.47 (s, 4H, 6-H), 3.38
(t, 4H, J7a,8a ¼ J7a,8b ¼ J7b,8a ¼ J7b,8b ¼ 7 Hz, 7-H), 2.03 (m, 4H, 8-H), 1.65
(m, 4H, 9-H). 13C NMR (50 MHz, CDCl3): ꢀ ¼ 152.1 (C-5), 130.5 (C-10),
110.5 (C-4), 67.4.(C-7), 64 (C-6), 28.3 (C-8), 28 (C-9). MS C14H20O3
(M:236): m/z ¼ 236 [M]þ; Anal. calcd. for C14H20O3 (9 minor þ 9 major):
C, 71.16; H, 8.53. Found: C, 70.89; H, 8.43.
ACKNOWLEDGMENTS
The participation of Sudzucker AG (Mannheim, Germany) in
¨
providing HMF is gratefully acknowedged.
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Received in the UK July 24, 2003

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