Syntheses, characterizations, and biological activities of tetradeca-4,8-dien-1-yl acetates as sex attractants of leaf-mining moth of the genus Phyllonorycter (Lepidoptera: Gracillariidae)

Article abstract of DOI:10.1002/cbdv.200800210

The four possible isomers of tetradeca-4,8-dien-1-yl acetate and corresponding alcohols were synthesized stereoselectively by synthetic routes employing Wittig coupling reaction for the preparation of (Z,E)- and (Z,Z)-isomers, and alkylation of terminal alkynes for the preparation of (E,E)- and (E,Z)-isomers as the key steps. Synthetic products were characterized by ¹³C- and ¹H-NMR spectroscopy as well as mass-spectrometric methods. All four isomers gave distinctive mass spectra where m/z 81 fragments clearly dominated. Elution order, followed by retention index presented in parenthesis, of tetradeca-4,8-dien-1-ols was determined as (Z,Z) (2082.1), (Z,E) (2082.8), (E,E) (2083.1), and (E,Z) (2083.2) from unpolar SPB-1 column, and as (E,E) (2210.2), (Z,E) (2222.1), (E,Z) (2223.4), and (Z,Z) (2224.7) from polar DB-WAX column. The isomers of tetradeca-4,8-dien-1-yl acetates eluted in the order of (Z,Z) (2176.1), (Z,E) (2178.4), (E,Z) (2185.9), and (E,E) (2186.4) from SPB-1, and (Z,E) (2124.3), (E,E) (2157.7), (Z,Z) (2128.9), and (E,Z) (2135.9) from DB-WAX columns. Field-screening tests for attractiveness of tetradeca-4,8-dien-1-yl acetates revealed that (4Z,8E)-tetradeca-4,8-dien-1-yl acetate significantly attracted Phyllonorycter coryli and Chrysoesthia drurella males. (4E,8E)-Tetradeca-4,8-dien-1-yl acetate was the most efficient attractant for Ph. esperella and Ph. saportella males, and (4E,8Z)-tetradeca-4,8-dien-1-yl acetate was attractive to Ph. cerasicolella males.

Full text of DOI:10.1002/cbdv.200800210

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CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
Syntheses, Characterizations, and Biological Activities of Tetradeca-4,8-dien-
1-yl Acetates as Sex Attractants of Leaf-Mining Moth of the Genus
Phyllonorycter (Lepidoptera: Gracillariidae)
by Ilme Liblikasa)b), Raimondas Mozuraitis*a)c), Ellen M. Santangeloa), Remigijus Noreikad), and
¯
Anna-Karin Borg-Karlsona)
a) Ecological Chemistry Group, Division of Organic Chemistry, Department of Chemistry, School of
Chemical Science and Engineering, Royal Institute of Technology, SE-10044 Stockholm
(fax: þ4687912333; e-mail: raimis@kth.se)
b) Institute of Technology, University of Tartu, Nooruse 1, EE-50411, Tartu
c) Laboratory of Chemical and Behavioural Ecology, Institute of Ecology, Vilnius University,
Akademijos 2, LT-2600 Vilnius
d) Department of Botany, Faculty of Natural Sciences, Vilnius Pedagogical University, LT-08106 Vilnius
The four possible isomers of tetradeca-4,8-dien-1-yl acetate and corresponding alcohols were
synthesized stereoselectively by synthetic routes employing Wittig coupling reaction for the preparation
of (Z,E)- and (Z,Z)-isomers, and alkylation of terminal alkynes for the preparation of (E,E)- and (E,Z)-
isomers as the key steps. Synthetic products were characterized by 13C- and 1H-NMR spectroscopy as well
as mass-spectrometric methods. All four isomers gave distinctive mass spectra where m/z 81 fragments
clearly dominated. Elution order, followed by retention index presented in parenthesis, of tetradeca-4,8-
dien-1-ols was determined as (Z,Z) (2082.1), (Z,E) (2082.8), (E,E) (2083.1), and (E,Z) (2083.2) from
unpolar SPB-1 column, and as (E,E) (2210.2), (Z,E) (2222.1), (E,Z) (2223.4), and (Z,Z) (2224.7) from
polar DB-WAX column. The isomers of tetradeca-4,8-dien-1-yl acetates eluted in the order of (Z,Z)
(2176.1), (Z,E) (2178.4), (E,Z) (2185.9), and (E,E) (2186.4) from SPB-1, and (Z,E) (2124.3), (E,E)
(2157.7), (Z,Z) (2128.9), and (E,Z) (2135.9) from DB-WAX columns. Field-screening tests for
attractiveness of tetradeca-4,8-dien-1-yl acetates revealed that (4Z,8E)-tetradeca-4,8-dien-1-yl acetate
significantly attracted Phyllonorycter coryli and Chrysoesthia drurella males. (4E,8E)-Tetradeca-4,8-
dien-1-yl acetate was the most efficient attractant for Ph. esperella and Ph. saportella males, and (4E,8Z)-
tetradeca-4,8-dien-1-yl acetate was attractive to Ph. cerasicolella males.
Introduction. – The tentiform leaf miner moths of the genus Phyllonorycter
belong to the family Gracillariidae, one of the oldest families within the taxo-
nomic group Ditrysia of Lepidoptera [1]. Attraction to light is the common mean to
collect specimens for biodiversity, zoogeographic, and taxonomic studies, how-
ever, moths from some taxonomic groups are poorly attracted or do not fly to
a light at all. Increasing data about sex attractants and pheromones of Lepid-
optera enable to use these infochemicals as a supplementary means for the collect-
ion of specimens especially for attraction of individuals from specific taxonomic
groups.
All together, 688 Phyllonorycter species are known throughout the world [2], so a
high chemodiversity of sex-pheromone components is expected. Nine compounds as
components of sex pheromones and 13 chemicals as sex attractants have been identified
ꢀ 2009 Verlag Helvetica Chimica Acta AG, Zꢁrich

CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
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for 19 and 17 species of the genus Phyllonorycter, respectively [3]. Sex pheromones and
most of the sex attractants consist of aliphatic, saturated, as well as mono-
and diunsaturated, linear, C12- and C14-chain acetates. Conjugated and non-conju-
gated C¼C bonds can occur at even positions from 4 to 12 in either (Z)- or (E)-
configuration.
A few years ago, the molecular phylogeny of 77 Phyllonorycter species was
published [4], which provided a good opportunity to compare the chemical pattern of
compounds used for search of a mate with the phylogeny of the genus. However, data
concerning sex attractants of Phyllonorycter are too scattered to be mapped onto the
moth phylogeny, and more efforts searching for new attractants including structurally
new compounds are needed.
Chemodiversity and biological aspects of mate search signals in the genus
Phyllonorycter have been studied by our group in over 15 years. Preliminary GC/MS
analyses of a few compounds released by calling females of some Phyllonorycter
species showed a fragmentation pattern that could be explained by a new tetradeca-
dien structure with respect to the positions of C¼C bonds. Taking into considera-
tion that all C¼C bonds of sex pheromone components known at present for
Phyllonorycter moths occur at even positions we predict C¼C bonds to occur at the
positions 4 and 8. In this article, we present syntheses, chemical characterizations, and
bioassay tests of all isomers of tetradeca-4,8-dien-1-ols and their acetates. To the best of
our knowledge, this is the first report about biological activity of tetradeca-4,8-dien-1-yl
acetates.
Results and Discussion. – Syntheses and Characterization of Compounds. The
effectiveness of synthesized attractants and pheromones in the field is influenced by
many factors, among these the chemical and isomeric purities of the (Z)- and (E)-
isomers play an important role. Thus, particular care must be paid to the regio- and
stereochemical control of the reactions used for the construction of such mole-
cules. There are two strategies in the synthesis of all four geometrical isomers of
dienes: one can synthesize each isomer in a stereoselective mode, or fix one C¼C bond
with the starting material and the other rather nonspecifically by a Wittig reaction
[5].
There are no data available in the literature characterizing the isomers of tetradeca-
4,8-dienyl acetates, neither elution order and retention indexes, nor NMR and mass
spectra. Therefore, it was necessary to synthesize all four isomers individually by stereo-
selective synthetic routes to ensure that the data we report here are in accordance with
those of the respective isomers they should characterize. Sketch of the possible retro-
synthetic pathways and checking the availability of building-block candidates for synthesis
of all four isomers of tetradeca-4,8-dienyl acetates revealed that the C¼C bond at the
position 8 can be fixed by the commercially available (E)- and (Z)-dec-4-enals, respec-
tively, whereas the C¼C bond at C(4) must be generated (E)- and (Z)-stereospecifi-
cally.
Wittig condensation between aldehydes and phosphonium salts is a well-known and
widely applicable method in pheromone synthesis. Although the stereoselectivity is not
very high, it can be accepted as a good method for the generation of (Z)-C¼C bonds
due to its simplicity and quite readily available synthons. The (E)-C¼C bond is not

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CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
readily accomplished by Wittig reaction, but via acetylenic route1). Accordingly, we
decided to synthesize the isomers of tetradeca-4,8-dienyl acetate with (4Z)-configu-
ration by Wittig reaction, and the isomers with (4E)-configuration via acetylenic
synthesis.
Synthesis of (4Z,8Z)- and (4Z,8E)-Tetradeca-4,8-dien-1-yl Acetates (1 and 2, resp.).
The (Z,Z)- and (Z,E)-isomers were synthesized by the Wittig coupling reaction under
conditions generating the new (Z)-C¼C bond stereospecifically [11–12]. The synthetic
route is shown in Scheme 1.
Scheme 1. Synthesis of (4Z,8Z)- and (4Z,8E)-Tetradeca-4,8-dienyl Acetates (1 and 2, resp.)
a) 3,4,5,6-Tetrahydro-2H-pyran (THP), CH2Cl2, Amberlyst-15. b) 1H-Imidazole, Ph3P, I 2, THF. c) Ph3P,
CaCO3, MeCN. d) Sodium hexamethyldisilazide (NaHMDS), THF, (Z)-dec-4-enal. e) MeOH,
Amberlyst-15. f) Ac2O, Py. g) NaHMDS, THF, (E)-dec-4-enal.
(4Z,8Z)-Isomer 1 was synthesized using the (Z)-selective silazide procedure
between {4-[(tetrahydropyran-2-yl)oxy]butyl}triphenylphosphonium iodide (5) and
(Z)-dec-4-enal. The phosphonium salt 5 was synthesized in three steps from butane-1,4-
diol2). One OH group of this diol was protected as THP-acetal, and the other was
converted to the I substituent using a known method with 1H-imidazole, Ph3P, and I2
1
)
There are examples of the Wittig reaction leading to the (E)-isomer as main product [6–10], but this
method is not reliable to build up a synthetic scheme using it as a step to introduce the (E)-C¼C
bond.
The initial synthetic plan exploited the phosphonium salt from 4-bromobutan-1-ol. Our attempts to
prepare (4-hydroxybutyl)(triphenyl)phosphonium bromide by routine manner from 4-hydroxybutyl
bromide and Ph3P failed completely due to the equilibrium generating THF and HBr from 4-
hydroxybutylbromide [13].
2
)

CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
1391
[14]. Treatment of 1-iodo-4-[(tetrahydropyran-2-yl)oxy]butane (4) with Ph3P in MeCN
yielded the phosphonium salt 5 which was coupled with (Z)-dec-4-enal using sodium
hexamethyldisilazide (NaHMDS) as a base to generate the phosphonium ylide. The
THP-protected alcohol 6 was converted to (4Z,8Z)-tetradeca-4,8-dien-1-ol (7) in the
presence of Amberlyst-15 in MeOH. Acetylation with Ac2O in pyridine yielded 1,
which was 99% isomerically pure after low temperature crystallization from hexane.
Condensation of the same phosphonium salt 5 with (E)-dec-4-enal under similar
conditions afforded, after deprotection and acetylation, the isomer 2 in a good isomeric
purity (98%).
Synthesis of (4E,8E)- and (4E,8Z)-Tetradeca-4,8-dien-1-yl Acetates (10 and 11,
resp.). For the synthesis of 10 and 11, two subsequent acetylenic couplings were
employed as shown in Scheme 2.
The bifunctionality of but-3-yn-1-ol and pent-4-yn-1-ol, easily accessible conve-
nient synthons for dienes with C¼C bonds separated by two CH2 groups, has been
exploited in the synthesis of (4E,8E)- and (4E,8Z)-tetradeca-4,8-dien-1-ols and
corresponding acetates. Non-3-yn-1-ol (15) or corresponding protected alcohol 14 is
a precursor for both (E)- and (Z)-non-3-enyl bromides, key compounds for the
synthesis of 10 and 11, respectively. We have employed two different acetylenic routes
for the synthesis of THP-protected non-3-yn-1-ol 14 (Scheme 2)3). The CꢀC bond was
reduced (E)-selectively with LiAlH4, or (Z)-selectively with dicyclohexylborane. Both
reductions offered the advantage of easy access either to geometrically pure (E)-
stereoisomers, or to (Z)-isomers having stereoisomeric purity higher than 99%.
Addition of (E)- and (Z)-1-bromo-3-nonenes (17 and 23, resp.) to the lithium
derivative of the THP-acetal of pent-4-yn-1-ol (18), and subsequent deprotection and
transformation of the corresponding (E)- and (Z)-isomeric enynes, 20 and 25,
respectively, into the dienes gives, after acetylation, (E,E)- and (E,Z)-isomers 10 and
11.
In the synthesis of Lepidoptera pheromones, the so-called ꢂacetyleneꢃ route is
frequently used, which consists of coupling alkali-metal alkynylides with alkyl halides
having an O-containing functional group in the w-position, followed by the stereo-
selective reduction of the CꢀC to a C¼C bond with the (Z)- or (E)-configuration. For
the reduction, there are numerous methods of choice yielding the product with high
stereoisomeric purity4).
3
)
Attempt to prepare 1-bromonon-3-yne directly from hept-1-yne and 1,2-dibromoethane [15] was
not so successful due to formation of a mixture of unreacted starting material, desired
monoalkylation product, and alkadiyne coupled from both ends of dibromide. The desired 1-
bromonon-3-yne was not easily separable from this mixture by chromatography.
Lindlar catalyst [16–18] is the most popular catalyst for the selective hydrogenation of alkynes to
(Z)-alkenes. Other methods leading the (Z)-alkenes are the use of Ni-P2 (borohydride-reduced
nickel) [19][20], Zn-Cu couple [21], or activated Zn powder [22][23], and the reduction with
borohydrides or dialkylboranes [24][25]. Generally, the reduction of acetylenes to the (E)-alkenes is
carried out using Li or Na in liquid NH3 [26][27]. LiAlH4 in Et2O or THF is used for long-chain alk-
2-ynes. For b-, g-, or w-alkynes, higher temperatures are needed for the reduction, and diglyme or a
mixture of diglyme and THF is the solvent of choice [28–31].
4
)

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CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
Scheme 2. Synthesis of (4E,8E)- and (4E,8Z)-Tetradecadienyl Acetates (10 and 11, resp.)
a) THP, Amberlyst-15, CH2Cl2. b) BuLi, THF, NaI, 1-bromopentane. c) BuLi, THF, NaI, hept-1-yne. d)
MeOH, Amberlyst-15. e) LiAlH4, diglyme. f) Ph3PBr2, CH2Cl2, Py. g) BuLi, NaI, THF. h) Ac2O, Py. i) 1)
Dicyclohexylborane (Cy2BH), THF, 2) AcOH, 3) NaOH, H2O2. j) Ph3PBr2, CH2Cl2.

CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
1393
Synthesis of all four isomers of 1,4-dienic alcohols can be accomplished via key
enynoic intermediates, which are obtained by two coupling reactions of acetylenides
with appropriate alkyl halides [15][29–30]5).
1H- and 13C-NMR Characterization of Tetradeca-4,8-dien-1-ols and Their Acetates.
1
The H-NMR spectra of the isomers of tetradeca-4,8-dien-1-ols and their acetates do
not sufficiently characterize the C¼C bonds while giving multiplets from 5.3 to 5.5 ppm
for each isomer. The 13C-NMR spectra differentiate between the compounds better,
showing different shifts for C¼C bond C-atoms. Comparison between 13C-NMR
chemical shifts (ppm) for the olefinic C-atoms of tetradeca-4,8-dien-1-ols and their
acetates is presented in the Figure.
GC/MS Characterization of Tetradeca-4,8-dien-1-ols and Their Acetates. The
isomers of tetradeca-4,8-dien-1-ols eluted in the order (Z,Z), (Z,E), (E,E), and
(E,Z) from an unpolar SPB-1 column, and in the order (E,E), (Z,E), (E,Z), and (Z,Z)
from a polar DB-WAX column (Table 1). The separation of all four alcohols on a SPB-1
column was very poor, while polar DB-WAX gave sufficient separation of 21 from 9,
which was found to be the next isomer in the elution sequence.
Table 1. Retention Indices of Tetradeca-4,8-dien-1-ols and Their Acetates Obtained Using Two Types of
GC Columns.
Compounds
Column type
SPB-1
DB-WAX
4Z,8Z-14 :OH (7)
4Z,8E-14 :OH (9)
4E,8Z-14 :OH (26)
4E,8E-14 :OH (21)
4Z,8Z-14 :OAc (1)
4Z,8E-14 :OAc (2)
4E,8Z-14 :OAc (11)
4E,8E-14 :OAc (10)
2082.1
2082.8
2083.2
2083.1
2176.1
2178.4
2185.9
2186.4
2224.7
2222.1
2223.4
2210.2
2126.9
2124.3
2135.9
2125.7
It was found that from the SPB-1 column, acetates eluted in pairs: the first one
included the (Z,Z)- and (Z,E)-isomers, and the second pair comprised (E,Z)- and
(E,E)-isomers. The separation between (E,Z)- and (E,E)-isomers was not sufficient.
The best separation of acetates was achieved by using a DB-WAX column.
Well-expressed base peaks at m/z 81 in the mass spectra of all tetradeca-4,8-dien-1-
ols and their acetates were specific for 4,8-dienes and provided an important diagnostic
5
)
There are many examples describing alkylations of acetylenes using bromides [32–42] or iodides
[43–46] as alkylating agent in THF in the presence of HMPA or HMPT leading to good-to-
excellent product yield. These co-solvents were successfully replaced by DMPU as a safer and
comparably efficacious alternative in the reactions with alkyl iodides [47]. Alkyl bromides in the
presence of DMPU gave poor or moderate yields and undesirable by-products [30–31][38][48–49].
Buck and Chong [50] showed that THF alone may be used. Bromides reacted much slower and gave
incomplete reactions compared to iodides. Therefore, addition of NaI or tetrabutylammonium
iodide accelerated the reaction to provide a good yield. Surveying the latest literature, one can find
that HMPA is still the most frequently used co-solvent despite the harmfulness and existence of
alternatives.

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CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
Figure. The 13C-NMR spectra of tetradeca-4,8-dien-1-ols and their acetates

CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
1395
feature of those structures. In addition, detectible diagnostic ion peaks at m/z 192
([Mꢁ60]) of tetradeca-4,8-dien-1-yl acetates and molecular-ion peak at m/z 210 of
tetradeca-4,8-dien-1-ols indicated di-unsaturation and a chain length of C14 [51]. The
absence of the pattern, when both molecular-ion peak and the peak at m/z 192 ([Mꢁ
60] for acetates and [Mꢁ18] for primary alcohols) are well expressed in the spectrum,
indicated that double bonds are present in a non-conjugated manner [52].
Field Tests. Phyllonorycter coryli (Nicelli, 1851) (Lepidoptera: Gracillariiidae). In
total, 99 males were captured (Table 2). 4Z,8E-14 :OAc (2) attracted 74 males and was
significantly the most efficient lure, followed by 4E,8E-14:OAc (10), which resulted in
catch of 25 males. The binary mixture of (Z)-tetradec-10-en-1-yl acetate and (E)-
tetradec-9-en-1-yl acetate in a ratio of 1:10 was previously reported as sex attractant
for the males of this species [53]. Taking into consideration that C¼C bonds of all
identified sex pheromones of Phyllonorycter occur at even positions, we can predict
that, in the compound used for chemical communication by moths of this species, the
(E)-C¼C bond is at position 8 instead of 9.
Table 2. Attraction of Males from the Genera Phyllonorycter and Chrysoesthia to Synthetic Tetradeca-
4,8-dien-1-yl Acetates under Field Tests
Compounds
Species
Ph. cora)
Ph. espb)
Ph. kuhc)
Ph. cerd)
Ch. drue)
4Z,8Z-14 :OAc (1)
4Z,8E-14 :OAc (2)
4E,8Z-14 :OAc (11)
4E,8E-14 :OAc (10)
Control
0
74 a
0
25 b
0
0
1 b
0
26 a
0
0
4 b
0
31 a
0
2 b
0
7 a
0
3 b
763 a
3 b
0
0
0
Total catch
99
27
35
9
769
a) Phyllonorycter coryli. b) Phyllonorycter esperella. c) Phyllonorycter kuhlweiniella. d) Phyllonorycter
cerasicolella. e) Chrysoesthia drurella. Control dispensers are loaded with solvent only. Each figure
denotes the total number of males attracted to five traps loaded with the compound indicated. The
differences between numbers in the column followed by different letters are statistically significant at p<
0.05 according to Duncanꢃs multiple range test.
Phyllonorycter esperella (Goeze, 1783). It has the synonym name Phyllonorycter
quinnata (Geoffrey, 1785). Traps containing 4E,8E-14 :OAc (10) caught 26 males of
27 attracted in total (Table 2). In conclusion, 10 has to be considered as the sex
attractant for the males of this species. As far as we know, this is the first report of sex
attractant for Ph. esperella species.
Phyllonorycter kuhlweiniella (Zeller, 1839) (Lepidoptera: Gracillariiidae). It has
the synonym name Phyllonorycter saportella (Duponchel, 1840). Thirty-one males of
this species were caught by the traps baited with 4E,8E-14 :OAc (10; Table 2). An
another four males were attracted to 4Z,8E-14 :OAc (2); however, the efficiency of the
lures was significantly lower compared with those of 10. Binary mixture of (E)-
tetradec-8-en-1-yl acetate and (E)-tetradec-10-en-1-yl acetate in a ratio of 1:1 was
reported as the sex attractant to the males of this species by Voerman [54].

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CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
In Lithuania, Ph. kuhlweiniella was known from one location only, and the results
from the field test revealed the second place where the moths of this species are
present.
Phyllonorycter cerasicolella (Herrich-Schꢀffer, 1855) (Lepidoptera: Gracillar-
iiidae). 4E,8Z-14 :OAc (11) pulled significantly higher number of males when
compared with attractiveness of 4Z,8Z-14 :OAc (1; Table 2). This species has a local
distribution in Lithuania [55], and low catches of the males could be attributed to
scantiness of specimens in the test area, as a few mines were found on leaves of cherry
trees after half an hour of inspection. In conclusion, 10 has to be considered as a sex
attractant for the males of this species. As far as we know, this is the first report of sex
attractant for Ph. cerasicolella species.
Chrysoesthia drurella (Fa b r i c i u s , 1775) (Lepidoptera: Gelechiidae). Traps con-
taining 4Z,8E-14 :OAc (2) caught 763 males of 769 attracted in total (Table 2). 4Z,8Z-
14 :OAc (1) and 4E,8Z-14 :OAc (11) attracted three males each, but their catches were
significantly lower compared with those of 4Z,8E-14 :OAc (2). Thus, 2 has to be
considered as sex attractant of Chrysoesthia drurella species. No attractants were
previously known for the species of the genus Chrysoesthia.
In conclusion, our data revealed that tetradeca-4,8-dien-1-yl acetates are novel sex
attractants of Lepidoptera. Despite the new diene structure with respect to the
positions of C¼C bonds, the structural pattern of tetradeca-4,8-dien-1-yl acetates
corresponds well to that known for the pheromones of genus Phyllonorycter. The C¼C
bond at the position 8 was reported in six compounds, all C14-chain acetates and
alcohols which are used for sex communication by moths of seven Phyllonorycter
species, and this position is the second most common one in the sex attractants and
pheromones of the genus [3]. Only one (4E,10E)-tetradeca-4,10-dien-1-yl acetate
bearing C¼C bond at the position 4 was identified as sex pheromone of Phyllonorycter
ringoniella (Matsumura). In addition, three other compounds, C12- and C13-chain
acetates, with the C¼C bond at the position 4 are known to attract moths of two
Phyllonorycter species.
Moreover, our recent preliminary results indicated that Ph. cerasicolella females
produce and release two tetradeca-4,8-dienes, which show that compounds of this type
function as sex pheromones. All four Phyllonorycter species, for which tetradeca-4,8-
dien-1-yl acetates are reported as sex attractants, belong to two closely related species
groups [4], and, if females of all these species produce sex pheromones of tetradeca-4,8-
dien type, the new species group with respect to pheromone structure could be defined.
This work was supported by Lithuanian State Grant (Isolation and identification of infochemicals
affecting organisms in ecosystems, study of regulatory mechanisms, elucidation of behavioral stimuli, and
assessment of their role in evolution) allocated to the Laboratory of Chemical and Behavioral Ecology at
the Institute of Ecology, Vilnius University, by Estonian Science Foundation (Grant No. GLOTI 7517,
GP1TI6520), Estonian Target Oriented Financing (Grant No. TLOTI 0073), the Swedish Research
Council (VR), and by the Swedish Institute (SI) via the Visby Program to the Nordic-Baltic network in
Ecological Chemistry.
Experimental Part
General. Chemicals were bought from Aldrich Chemical Co. and Alfa Aesar; they were used as
purchased. THF was distilled from Na/benzophenone. Reactions involving anh. solvents were carried out
under Ar or N2. The phrase ꢂusual workupꢃ describes the following sequence: reaction mixture poured

CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
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into H2O, org. compounds extracted 3ꢂ into hexane, combined hexane fractions washed with brine and
H2O, dried (anh. MgSO4), and concentrated in rotary evaporator. Medium-pressure liquid chromatog-
raphy (MPLC) [56] was performed on SiO2 (Merck 60, 0.040–0.063 mm) in 15- or 35-mm i.d. glass
columns with gradient elution, using hexane and increasing proportions of AcOEt. For isomeric
purification, AgNO3 impregnated SiO2 was used (20% of AgNO3 by weight was used to impregnate SiO2
in a H2O/EtOH soln.). The slurry was evaporated to dryness in a rotary evaporator and finally activated
in an oven at 1108 for 5 h [57].
1H- and 13C-NMR spectra of synthetic intermediates as well as of the products were recorded in
CDCl3 solns. at 400, 500, or 125.8 MHz, resp., with Bruker AM 400 or AM 500 NMR spectrometers.
Synthesized dienic alcohols and acetates were analyzed on the GC/MS system consisting of Varian
3400 gas chromatograph (GC) and Finnigan SSQ 7000 mass spectrometer (MS). One SPB-1 and one
DB-WAX SiO2 cap. column (both 30-m length, 0.25-mm i.d. and 0.25-mm film thickness) were used with a
temp. program of 408 (1 min), increased by 108/min to 1408, then by 18/min up to 1648, then by 108/min up
to 2308, and thereafter maintained constant at 2308 for 7 min. The split/splitless injector temp. was 2258,
and the splitless period was 30 s. He was used as the carrier gas with an inlet pressure of 70 kPa. Electron
ionization (EI) mass spectra were recorded at 70 eV with the ion source at 1508; in m/z (rel. intensity).
Syntheses of Tetradeca-4,8-dien-1-yl Acetates. 4-[(Tetrahydropyran-2-yl)oxy]butan-1-ol (3) [58]. To
a stirred soln. of butane-1,4-diol (20.0 g, 0.22 mol) and Amberlyst-15 (0.5 g) in CH2Cl2 (200 ml), DHP
(18.67 g, 0.22 mol) was added, and the mixture was stirred for 4 h at r.t. The catalyst was filtered off, and
1
the mixture was adsorbed on SiO2 before MPLC, which yielded 3 (22.0 g, 57.5%). H-NMR (400 MHz,
CDCl3): 4.59 (dd, J¼4.9, 2.7, HꢁC(2’)); 3.83–3.89 (m, HbꢁC(6’)); 3.80 (dt, J¼10.1, 6.3, HbꢁC(4)); 3.66
(t, J¼7.0, 2 HꢁC(1)); 3.46–3.53 (m, HaꢁC(6’)); 3.42 (dt, J ¼ 9.7, 5.6, HaꢁC(4)); 2.17 (br. s, OH); 1.48–
1.87 (m, 2 HꢁC(2), 2 HꢁC(3), 2 HꢁC(3’), 2 HꢁC(4’), 2 HꢁC(5’)).
1-Iodo-4-[(tetrahydropyran-2-yl)oxy]butane (4) [13][59]. To a soln. of 3 (20.88 g, 120 mmol) in THF
(320 ml), Ph3P (44.8 g, 171 mmol) and 1H-imidazole (24.5 g, 360 mmol) were successively added under
N2 at r.t. The soln. was cooled to ꢁ308, and I2 (42.6 g, 168 mmol) was added in one portion. The mixture
was stirred at r.t. for 2 h and then poured into H2O. The products were extracted with hexane, washed
with H2O and a sat. soln. of Na2S2O3, dried, and concentrated. MPLC gave 4 (31.2 g, 91.5%). 1H-NMR
(500 MHz, CDCl3): 4.55 (t, J¼3.5, HꢁC(2’)); 3.81–3.86 (m, HbꢁC(6’)); 3.75 (dt, J¼9.8, 6.4, HbꢁC(4));
3.47–3.51 (m, HaꢁC(6’)); 3.40 (dt, J¼9.8, 6.2, HaꢁC(4)); 3.22 (t, J¼7.0, 2 HꢁC(1)); 1.46–1.96 (m,
2 HꢁC(2), 2 HꢁC(3), 2 HꢁC(3’), 2 HꢁC(4’), 2 HꢁC(5’)). 13C-NMR (125.8 MHz, CDCl3): 98.8
(C(2’)); 66.3 (C(6’)); 62.3 (C(4)); 30.7 (C(3’)); 30.6 (C(3)); 30.5 (C(2)); 25.4 (C(5’)); 19.6 (C(4’)); 6.8
(C(1)).
{4-[(Tetrahydropyran-2-yl)oxy]butyl}(triphenyl)phosphonium Iodide (5) [13]. A soln. containing 4
(34.2 g, 120 mmol), Ph3P (41.9 g, 160 mmol), and CaCO3 (6 g) in MeCN (200 ml) was heated at 708 for
50 h. CaCO3 was filtered off, and the solvent was evaporated in vacuo. Residue was dissolved in a
minimum amount of CH2Cl2, and dilution with Et2O led to the precipitation of 5 (56.5 g, 86%).
(4Z,8Z)-1-[(Tetrahydropyran-2-yl)oxy]tetradeca-4,8-diene (6) [12][60]. A soln. of 5 (19.6 g,
36 mmol) in dry THF (200 ml) was treated at 08 with NaHMDS (2m soln. in THF; 18 ml, 36 mmol),
and the resulting red soln. was stirred for 1.5 h at r.t. The soln. was then cooled to ꢁ788, and (Z)-dec-4-
enal (5.0 g, 32.5 mmol) in THF (5 ml) was added dropwise. The mixture was allowed to warm to r.t.,
stirred overnight, and then poured into sat. aq. NH4Cl soln. Org. compounds were extracted with hexane.
The soln. was dried (MgSO4) and chilled to precipitate most of the Ph3PO. After filtration, the filtrate
was concentrated and chromatographed on SiO2 to give 6 (8.21 g, 86.4%). 1H-NMR (500 MHz, CDCl3):
5.32–5.44 (m, HꢁC(4), HꢁC(5), HꢁC(8), HꢁC(9)); 4.56–4.58 (m, HꢁC(2’)); 3.84–3.89 (m,
HbꢁC(6’)); 3.74 (dt, J¼9.7, 6.7, HbꢁC(1)); 3.46–3.66 (m, HaꢁC(6’)); 3.38 (dt, J¼9.7, 6.7, HaꢁC(1));
1.99–2.17 (m, 2 HꢁC(3), 2 HꢁC(6), 2 HꢁC(7), 2 HꢁC(10)); 1.48–1.72 (m, 8 H; HꢁC(3’), HꢁC(4’)
HꢁC(5’), HꢁC(2)); 1.23–1.37 (m, 6 H; HꢁC(11), HꢁC(12), HꢁC(13)); 0.88 (t, J¼7.0, 3 H;
HꢁC(14)). 13C-NMR (125.8 MHz, CDCl3): 130.4; 129.8; 129.4; 129.0; 98.8; 67.0; 62.3; 31.5; 30.8; 29.8;
29.4; 27.4; 27.3; 27.2; 25.5; 23.9; 22.6; 19.7; 14.1.
(4Z,8Z)-Tetradeca-4,8-dien-1-ol (7) [58]. A soln. of 6 (8.20 g, 21 mmol) in MeOH (35 ml) was stirred
in the presence of Amberlyst-15 (0.5 g) at 508 for 4 h. The catalyst was filtered off, and the solvent
evaporated. MPLC yielded 7 (5.63 g, 96.2%). 1H-NMR (500 MHz, CDCl3): 5.33–5.45 (m, HꢁC(4),

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CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
HꢁC(5), HꢁC(8), HꢁC(9)); 3.65 (t, J¼6.5, 2 HꢁC(1)); 2.06–2.16 (m, 2 HꢁC(3), 2 HꢁC(6),
2 HꢁC(7)); 1.99–2.05 (m, 2 HꢁC(10)); 1.63 (dt, J¼13.9, 6.5, 2 HꢁC(2)); 1.44 (br. s, OH); 1.23–1.37 (m,
2 HꢁC(11), 2 HꢁC(12), 2 HꢁC(13)); 0.88 (t, J¼7.0, 3 HꢁC(14)). 13C-NMR (125.8 MHz, CDCl3):
.
130.5; 130.1; 129.3; 128.9; 62.6; 32.6; 31.5; 29.4; 27.4; 27.3; 27.2; 23.6; 22.6; 14.1. MS (70 eV): 210 (2, Mþ ),
192 (0.4), 167 (1), 151 (2), 149 (1), 138 (6), 135 (4), 121 (10), 110 (9), 107 (5), 99 (7), 96 (8), 95 (12), 93
(7), 91 (2), 82 (20), 81 (100), 79 (22), 77 (3), 69 (48), 67 (21), 61 (0), 57 (10), 55 (50), 53 (10), 43 (19), 41
(51), 39 (11), 31 (7).
(4Z,8Z)-Tetradeca-4,8-dien-1-yl Acetate (1). Compound 7 (4.4 g, 21 mmol) was acetylated with Ac2O
(4.59 g, 45 mmol) in dry pyridine (25 ml) by keeping the reaction mixture in refrigerator (2–48)
overnight. Usual workup gave 1 (4.80g, 91%). 1H-NMR (500 Mz, CDCl3): 5.32–5.45 (m, HꢁC(4),
HꢁC(5), HꢁC(8), HꢁC(9)); 4.05 (t, J¼6.6, 2 HꢁC(1)); 2.10–2.13 (m, 2 HꢁC(3)); 2.05–2.08 (m,
2 HꢁC(6), 2 HꢁC(7)); 2.04 (s, MeCO); 1.97–2.02 (m, 2 HꢁC(10)); 1.68 (dt, J¼14.6, 7.6, 2 HꢁC(2));
1.22–1.37 (m, 2 HꢁC(11), 2 HꢁC(12), 2 HꢁC(13)); 0.88 (t, J¼7.0, 3 HꢁC(14)). 13C-NMR (125.8 MHz,
CDCl3): 171.1; 130.5; 130.4; 128.9; 128.5; 64.0; 31.5; 29.4; 28.5; 27.3; 27.23; 27.20; 23.6; 22.5; 21.0; 14.0. MS
.
(70 eV): 252 (0.5, Mþ ), 192 (10), 167 (0), 151 (2), 149 (4), 138 (3), 135 (14), 121 (20), 110 (10), 107 (7),
99 (1), 96 (5), 95 (9), 93 (9), 91 (2), 82 (23), 81 (100), 79 (22), 77 (2), 69 (32), 67 (22), 61 (1), 57 (4), 55
(30), 53 (6), 43 (51), 41 (33), 39 (8), 31 (0).
(4Z,8E)-1-[(Tetrahydropyran-2-yl)oxy]tetradeca-4,8-diene (8). Compound 8 was prepared analo-
gously to 6. A soln. of 5 (19.6 g, 36 mmol) in dry THF (200 ml) was treated with NaHMDS (2m soln. in
THF, 20 ml, 40 mmol) at 08. The mixture was stirred for 1.5 h at r.t. before it was cooled to ꢁ788, and
treated with (E)-dec-4-enal (4.86 g, 31.6 mmol) in THF (5 ml). The mixture was allowed slowly to warm
to r.t. and stirred overnight before pouring into sat. aq. NH4Cl soln. After workup similar to that for 6, the
crude product was chromatographed on SiO2 to give 8 (7.48 g, 80.6%). 13C-NMR (125.8 MHz, CDCl3):
130.8; 129.8; 129.6; 129.3; 98.8; 67.0; 62.3; 32.7; 32.5; 31.4; 30.8; 29.7; 29.3; 27.3; 25.5; 23.9; 22.5; 19.6; 14.1.
(4Z,8E)-Tetradeca-4,8-dien-1-ol (9). Compound 8 (7.25 g, 24.6 mmol) was stirred in MeOH (30 ml)
at 508 in the presence of Amberlyst-15 for 5 h. The catalyst was filtered off, and the residue yielded 9
1
(4.92 g, 95.2%) after MPLC. H-NMR (500 Mz, CDCl3): 5.35–5.45 (m, HꢁC(4), HꢁC(5), HꢁC(8),
HꢁC(9)); 3.65 (t, J¼6.5, 2 HꢁC(1)); 2.08–2.15 (m, 2 HꢁC(6), 2 HꢁC(7)); 2.01–2.06 (m, 2 HꢁC(3));
1.94–1.99 (m, 2 HꢁC(10)); 1.63 (dt, J¼14.0, 6.6, 2 HꢁC(2)); 1.45 (br. s, OH); 1.22–1.37 (m, 2 HꢁC(11),
2 HꢁC(12), 2 HꢁC(13)); 0.88 (t, J¼7.0, 3 HꢁC(14)). 13C-NMR (125.8 MHz, CDCl3): 131.0; 130.1;
.
129.5; 129.1; 62.6; 32.62; 32.56; 32.54; 31.4; 29.3; 27.4; 23.6; 22.5; 14.1. MS (70 eV): 210 (1, Mþ ), 192
(0.5), 167 (1), 151 (2), 149 (1), 138 (8), 135 (7), 121 (10), 110 (12), 107 (4), 99 (9), 96 (8), 95 (12), 93 (6),
91 (2), 82 (20), 81 (100), 79 (22), 77 (3), 69 (80), 67 (20), 61 (0), 57 (11), 55 (64), 53 (10), 43 (20), 41 (55),
39 (12), 31 (7).
(4Z,8E)-Tetradeca-4,8-dien-1-yl Acetate (2). Alcohol 9 (4.86 g, 23 mmol) in pyridine (30 ml) was
mixed with Ac2O (5.1 g, 50 mmol) at 08 and kept in refrigerator overnight. Usual workup and MPLC
yielded 2 (4.88 g, 83.7%). 1H-NMR (500 Mz, CDCl3): 5.31–5.45 (m, HꢁC(4), HꢁC(5), HꢁC(8),
HꢁC(9)); 4.05 (t, J¼6.7, 2 HꢁC(1)); 1.94–2.12 (m, 2 HꢁC(3), 2 HꢁC(6), 2 HꢁC(7), 2 HꢁC(10));
2.04 (s, MeCO); 1.67 (dt, J¼11.6, 6.5, 2 HꢁC(2)); 1.22–1.36 (m, 2 HꢁC(11), 2 HꢁC(12), 2 HꢁC(13));
0.88 (t, J¼7.0, 3 HꢁC(14)). 13C-NMR (125.8 MHz, CDCl3): 171.1; 131.0; 130.4; 129.4; 128.3; 64.0; 32.6;
.
32.5; 31.4; 29.2; 28.5; 27.3; 23.6; 22.5; 21.0; 14.0. MS (70 eV): 252 (0.7, Mþ ), 192 (11), 167 (0), 151 (2),
149 (4), 138 (3), 135 (12), 121 (20), 110 (13), 107 (6), 99 (1), 96 (5), 95 (9), 93 (9), 91 (2), 82 (32), 81
(100), 79 (20), 77 (2), 69 (51), 67 (24), 61 (1), 57 (5), 55 (37), 53 (5), 43 (52), 41 (35), 39 (8), 31 (0).
1-[(Tetrahydropyran-2-yl)oxy]but-3-yne (12) [58]. Compound 12 was prepared from but-3-yn-1-ol in
93% yield similarly to procedure described for 3.
1-[(Tetrahydropyran-2-yl)oxy]non-3-yne (14) [50]. Method 1. Compound 12 (7.70 g, 50 mmol) in
THF (80 ml) was lithiated with BuLi at ꢁ308. The bath temp. was allowed to rise to r.t., and the mixture
was stirred for 30 min before returning to ꢁ308. Pentyl bromide (9.06 g, 60 mmol) in THF (40 ml) along
with NaI (0.9 g, 6 mmol) was added. The mixture was gently refluxed and stirred for 16 h before it was
cooled and poured into ice-water. Usual workup and MPLC yielded 14 (8.90 g, 79%).
Method 2. Hept-1-yne (6.72 g, 70 mmol) in THF (180 ml) was lithiated by BuLi (28 ml of 2.5m soln.
in hexanes, 70 mmol) at ꢁ408. After stirring for 30 min at r.t., the mixture was cooled to ꢁ408 again.
Bromide 13 (12.5 g, 60 mmol) in THF (10 ml) was added along with NaI (1.5 g, 10 mmol), and the

CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
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1
mixture was refluxed for 12 h. Usual workup and MPLC yielded 14 (12.2 g, 91%). H-NMR (500 Mz,
CDCl3): 4.66 (t, J¼3.4, 1 H); 3.88–3.92 (m, 1 H); 3.78–3.82 (m, 1 H); 3.50–3.56 (m, 2 H); 2.44–2.48 (m,
2 H); 2.12–2.16 (m, 2 H), 1.77–1.87 (m, 1 H); 1.64–1.74 (m, 1 H); 1.45–1.63 (m, 6 H); 1.27–1.37 (m,
4 H); 0.90 (t, J¼7.1, 3 H ) .
Non-3-yn-1-ol (15). Compound 14 (6.60 g, 29 mmol) was deprotected by stirring in MeOH (45 ml)
along with Amberlyst-15 as described for compound 6. MPLC yielded alcohol 15 (3.44 g, 84%).
(E)-Non-3-en-1-ol (16) [28][35]. LiAlH4 (4.7 g, 123 mmol) was added portionwise to ice-cooled
diglyme (65 ml). After bubbling ceased, the soln. of 15 (5.60 g, 40 mmol) in diglyme (15 ml) was slowly
added to the ice-cooled slurry. Temp. was raised, and the mixture was stirred at 140–1458 for 5 h and then
cooled in an ice-bath. The reaction was quenched with Baeckstrçmꢃs reagent. Solids were filtered off, and
the resulting soln. was diluted with hexane (250 ml) and washed with H2O (3ꢂ100 ml) to remove most of
the diglyme. The hexane layer was dried (MgSO4), concentrated, and chromatographed. MPLC yielded
16 (5.17 g, 91%). 1H-NMR (500 MHz, CDCl3): 5.53 (dt, J¼15.3, 6.8, olef. H); 5.36 (dt, J¼15.3, 7.0, olef.
H); 3.60 (t, J¼6.3, 2 HꢁC(1)); 2.22–2.27 (m, 2 HꢁC(2)); 1.95–2.01 (m, 2 HꢁC(5)); 1.74 (br. s, OH);
1.21–1.37 (m, 2 HꢁC(6), 2 HꢁC(7), 2 HꢁC(8)); 0.87 (t, J¼7.0, 3 HꢁC(9)). 13C-NMR (125.8 MHz,
CDCl3): 134.2; 125.6; 59.0; 35.9; 32.6; 31.3; 29.1; 22.5; 14.0.
(E)-1-Bromonon-3-ene (17) [61]. Ph3PBr2 reagent was prepared in situ by adding Br2 (17.8 g,
111 mmol) in CH2Cl2 (10 ml) to an ice-cooled soln. of Ph3P (36.4 g, 139 mmol) in CH2Cl2 (200 ml).
Pyridine (10 ml) and 16 (11.3 g, 80 mmol) in CH2Cl2 (10 ml) were added to the resulting suspension while
cooled in an ice-bath. The mixture was stirred at r.t. for 2 h and poured into H2O. Org. compounds were
extracted with hexane. Hexane soln. was dried (MgSO4) and chilled to precipitate most of the Ph3PO.
After filtration, the filtrate was concentrated and subjected to MPLC to yield 17 (15.0 g, 92%). 1H-NMR
(500 Mz, CDCl3): 5.54 (dt, J¼14.1, 7.0, olef. H); 5.38 (dt, J¼15.3, 6.8, olef. H); 3.36 (t, J¼7.2, 2 HꢁC(1));
2.54 (dt, J¼7.1, 6.9, 2 HꢁC(2)); 2.00 (dt, J¼7.0, 6.8, 2 HꢁC(5)); 1.23–1.43 (m, 2 HꢁC(6), 2 HꢁC(7),
2 HꢁC(8)); 0.89 (t, J¼7.0, 3 HꢁC(9)). 13C-NMR (125.8 MHz, CDCl3): 134.0; 126.3; 36.1; 32.9; 32.5;
31.3; 29.0; 22.5; 14.0.
1-[(Tetrahydropyran-2-yl)oxy]pent-4-yne (18) [58]. Compound 18 prepared in the same manner as
12. DHP (14.7 g, 175 mmol) was added to pent-4-yn-1-ol (12.6 g, 150 mmol) in CH2Cl2 (120 ml)
containing Amberlys-15 as a catalyst. The mixture was stirred for 6 h at r.t., the catalyst was filtered off,
1
and the solvent was evaporated. MPLC yielded 18 (23.3 g, 92%). H-NMR (500 MHz, CDCl3): 4.58 (t,
J¼3.5, 1 HꢁC(2’)); 3.79–3.88 (m, 2 HꢁC(6’)); 3.45–3.51 (m, 2 HꢁC(1)); 2.33 (dt, J¼7.3, 2.6,
2 HꢁC(3)); 1.93 (t, J¼2.7, HꢁC(5)); 1.41–1.85 (m, 2 HꢁC(2), 2 HꢁC(3’), 2 HꢁC(4’), 2 HꢁC(5’)).
13C-NMR (125.8 MHz, CDCl3): 98.8; 83.9; 68.4; 65.7; 62.2; 30.6; 28.7; 25.4; 19.5; 15.3.
(E)-1-[(Tetrahydropyran-2-yl)oxy]tetradec-8-en-4-yne (19) [50]. Alkyne 18 (8.5 g, 50.6 mmol) in
THF (180 ml) was metallated with BuLi (22.3 ml 2.5m in hexanes; 56 mmol) at ꢁ308. The mixture was
warmed up to r.t. and stirred for additional 30 min. The resulting lithium acetylide was alkylated by
adding 17 (10.45 g, 54 mmol) along with NaI (2 g) at ꢁ308. The mixture was refluxed for 16 h and
followed by TLC. After 16 h, no more change in the starting alkyne product ratio was observed. Workup
and MPLC yielded 19 (9.44 g) along with some starting alkyne. The product was used in next step without
further purification.
(E)-Tetradec-8-en-4-yn-1-ol (20). Crude product from the previous reaction was deprotected in
MeOH in the presence of Amberlyst-15. MPLC yielded 20 (3.97 g, 19 mmol, 37.5% after two steps).
1H-NMR (500 MHz, CDCl3): 5.39–5.49 (m, 2 HꢁC(8), HꢁC(9)); 3.75 (t, J¼6.1, 2 HꢁC(1)); 2.26–2.29
(m, 2 HꢁC(7)); 2.13–2.21 (m, 2 HꢁC(3), 2 HꢁC(6)); 1.96–2.00 (m, 2 HꢁC(10)); 1.73 (dt, J¼12.4, 6.7,
2 HꢁC(2)); 1.63 (br. s, OH); 1.22–1.37 (m, 2 HꢁC(11), 2 HꢁC(12), 2 HꢁC(13)); 0.88 (t, J¼7.0,
3 HꢁC(14)). 13C-NMR (125.8 MHz, CDCl3): 131.8; 128.3; 80.7; 79.6; 62.1; 32.5; 32.2; 31.5; 31.4; 29.2;
22.5; 19.2; 15.4; 14.1.
(4E,8E)-Tetradeca-4,8-dien-1-ol (21). Reduction of the CꢀC-bond in 20 was achieved analogously
to that in 15. To a cooled suspension of LiAlH4 (3.88 g, 102 mmol) in diglyme (50 ml), 20 (3.1 g,
15 mmol) in diglyme (10 ml) was added, and the mixture was heated at 140–1458 for 6 h. After cooling,
the reaction was quenched with Bæckstrçmꢃs reagent. MPLC yielded 21 (2.4 g, 76.7%). 1H-NMR
(500 MHz, CDCl3): 5.35–5.48 (m, HꢁC(4), HꢁC(5), HꢁC(8), HꢁC(9)); 3.65 (t, J¼6.2, 2 HꢁC(1));
2.05–2.10 (m, 2 HꢁC(3)); 2.02–2.05 (m, 2 HꢁC(6), 2 HꢁC(7)); 1.94–1.99 (m, 2 HꢁC(10)); 1.63 (dt,

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CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
J¼13.8, 6.8, 2 HꢁC(2)); 1.47 (br. s, OH); 1.22–1.37 (m, 2 HꢁC(11), 2 HꢁC(12), 2 HꢁC(13)); 0.88 (t,
J¼7.0, 3 HꢁC(14)). 13C-NMR (125.8 MHz, CDCl3): 130.8; 130.6; 129.7; 129.5; 62.5; 32.7; 32.6; 32.5; 32.4;
.
31.4; 29.3; 28.9; 22.5; 14.1. MS (70 eV): 210 (1, Mþ ), 192 (0.3), 167 (1), 151 (1), 149 (1), 138 (6), 135 (2),
121 (6), 110 (10), 107 (2), 99 (10), 96 (4), 95 (7), 93 (3), 91 (1), 82 (14), 81 (100), 79 (16), 77 (2), 69 (50),
67 (13), 61 (0), 57 (8), 55 (42), 53 (8), 43 (14), 41 (39), 39 (9), 31 (6).
(4E,8E)-Tetradeca-4,8-dien-1-yl Acetate (10). To an ice-cooled soln. of 21 (1.77 g, 8.4 mmol) in dry
pyridine (10 ml), Ac2O (1.84 g, 18 mmol) was added, and the mixture was kept in a refrigerator
1
overnight. Workup and MPLC yielded 19 (1.93 g, 91 %). H-NMR (500 MHz, CDCl3): 5.35–5.46 (m,
HꢁC(4), HꢁC(5), HꢁC(8), HꢁC(9)); 4.05 (t, J¼6.6, 2 HꢁC(1)); 2.00–2.10 (m, 2 HꢁC(3),
2 HꢁC(6), 2 HꢁC(7)); 2.04 (s, MeCO); 1.92–1.99 (m, 2 HꢁC(10)); 1.68 (dt, J¼13.5, 6.6, 2 HꢁC(2));
1.22–1.37 (m, 2 HꢁC(11), 2 HꢁC(12), 2 HꢁC(13)); 0.88 (t, J¼7.0, 3 HꢁC(14)). 13C-NMR (125.8 MHz,
CDCl3): 170.8; 130.8; 130.7; 129.3; 128.8; 63.8; 32.54; 32.47; 32.41; 31.2; 29.2; 28.7; 28.3; 22.4; 20.7; 13.9.
.
MS (70 eV): 252 (0.3, Mþ ), 192 (7), 167 (0), 151 (1), 149 (3), 138 (3), 135 (10), 121 (14), 110 (11), 107
(4), 99 (1), 96 (3), 95 (6), 93 (5), 91 (1), 82 (22), 81 (100), 79 (14), 77 (1), 69 (33), 67 (15), 61 (1), 57 (4),
55 (25), 53 (5), 43 (38), 41 (26), 39 (6), 31 (0).
1-Bromo-2-[(tetrahydropyran-2-yl)oxy]ethane (13) [58]. 2-Bromoethanol (24.0 g, 192 mmol) and
DHP (17.6 g, 210 mmol) in CH2Cl2 (150 ml) were stirred in the presence of Amberlyst-15 at r.t. for 5 h.
Catalyst was filtered off, and the solvent was evaporated. MPLC yielded 13 (34.9 g, 87%).
(Z)-1-[(Tetrahydropyran-2-yl)oxy]non-3-ene (22) [15][48]. Borane-methylsulfide complex
(12.2 ml, 10m in THF, 122 mmol) was added to a soln. of cyclohexene (20.0 g, 244 mmol) in THF
(100 ml) while cooling in an ice-bath. The resulting suspension was stirred at r.t. for 2 h and cooled to ꢁ
308 before 14 (13.0 g, 58 mmol) was added. After 5 h at r.t., the mixture was treated with glacial AcOH
(40 ml) and stirred overnight at 508. Oxidation of the resulting dicyclohexyl borinate was achieved by
adding of NaOH (5n, 110 ml), followed by careful addition of H2O2 (35%, 40 ml) at a rate maintaining
the mixture at 30–358. Workup and MPLC yielded 22 (9.54 g, 73.6%). 13C-NMR (125.8 MHz, CDCl3):
132.0; 125.4; 98.7; 67.1; 62.3; 31.5; 30.7; 29.3; 27.9; 27.3; 25.5; 22.5; 19.6; 14.0.
(Z)-1-Bromonon-3-ene (23) [62]. Ph3PBr2 prepared in situ by adding Br2 (9.04 g, 56.5 mmol) in
CH2Cl2 (5 ml) to ice-cooled soln. of Ph3P (16.1 g, 61.5 mmol) in CH2Cl2 (100 ml). After stirring for 2 h, 22
(9.4 g, 41.6 mmol) in CH2Cl2 (10 ml) was added dropwise. The mixture was allowed to warm to r.t., and
stirring was continued for 4 h. Workup as described for 17 and MPLC yielded 23 (7.6 g, 95%).
(Z)-1-[(Tetrahydropyran-2-yl)oxy]tetradec-8-en-4-yne (24) [50]. Compound 24 was prepared by a
procedure similar to that used for of 19. Alkyne 18 (6.5 g, 39 mmol) in THF (120 ml) was deprotonated
by adding BuLi (15.6 ml, 2.5m in hexanes; 39 mmol) at ꢁ308. The mixture was warmed up to r.t. and
stirred for additional 30 min before bromide 23 (7.5 g, 39 mmol) was added along with NaI (2.0 g). The
mixture was refluxed for 18 h. The reaction was followed by TLC. After 18 h, no more change in starting
alkyne/product ratio was observed. Workup and MPLC yielded 24 (8.3 g) along with some starting
alkyne. The product was used in the next step without further purification.
(Z)-Tetradec-8-en-4-yn-1-ol (25). Deprotection of 24 (8.3 g, 28 mmol) in MeOH (25 ml) using
Amberlyst-15 as a catalyst yielded 25 (4.2 g, 71%). 1H-NMR (500 Mz, CDCl3): 5.36–5.46 (m, 2 HꢁC(8),
HꢁC(9)); 3.75 (t, J¼6.1, 2 HꢁC(1)); 2.27 (tt, J¼6.9, 2.3, 2 HꢁC(7)); 2.14–2.22 (m, 2 HꢁC(3),
2 HꢁC(6)); 2.03 (dt, J¼7.1, 7.0, 2 HꢁC(10)); 1.73 (q, J¼6.4, 2 HꢁC(2)); 1.68 (br. s, OH); 1.23–1.37 (m,
2 HꢁC(11), 2 HꢁC(12), 2 HꢁC(13)); 0.88 (t, J¼6.9, 3 HꢁC(14)). 13C-NMR (125.8 MHz, CDCl3):
131.4; 127.9; 80.7; 79.5; 62.1; 31.6; 31.5; 29.4; 27.3; 27.0; 22.6; 19.2; 15.5; 14.1.
(4E,8Z)-Tetradeca-4,8-dien-1-ol (26). LiAlH4 (2.47 g, 65 mmol) was added to ice-cooled diglyme
(30 ml), followed by 25 (2.5 g, 12 mmol) in diglyme (5 ml). The mixture was stirred at 1508 for 6 h, and
the reaction was quenched by adding Baeckstrçmꢃs reagent. Workup and MPLC yielded 26 (2.17 g, 86%).
1H-NMR (500 Mz, CDCl3): 5.30–5.46 (m, HꢁC(4), HꢁC(5), HꢁC(8), HꢁC(9)); 3.65 (t, J¼6.4,
2 HꢁC(1)); 1.98–2.11 (m, 2 HꢁC(3), 2 HꢁC(6), 2 HꢁC(7), 2 HꢁC(10)); 1.63 (dt, J¼13.6, 6.6,
2 HꢁC(2)); 1.55 (br. s, OH); 1.23–1.37 (m, 2 HꢁC(11), 2 HꢁC(12), 2 HꢁC(13)); 0.88 (t, J¼7.0,
3 HꢁC(14)). 13C-NMR (125.8 MHz, CDCl3): 130.4; 130.3; 129.8; 128.9; 62.4; 32.6; 32.3; 31.4; 29.3; 28.8;
.
27.19; 27.15; 22.5; 14.0. MS (70 eV): 210 (1, Mþ ), 192 (0.2), 167 (1), 151 (1), 149 (1), 138 (8), 135 (3), 121
(6), 110 (7), 107 (3), 99 (9), 96 (4), 95 (7), 93 (3), 91 (1), 82 (14), 81 (100), 79 (17), 77 (2), 69 (29), 67
(13), 61 (0), 57 (7), 55 (32), 53 (7), 43 (13), 41 (35), 39 (8), 31 (6).

CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
1401
(4E,8Z)-Tetradeca-4,8-dien-1-yl Acetate (11). Alcohol 26 (1.57 g, 7.5 mmol) was acetylated with
Ac2O (1.53 g, 15 mmol) in pyridine (10 ml) at 08 for 12 h. Workup and MPLC yielded 11 (1.55 g, 82%).
1H-NMR (500 Mz, CDCl3): 5.30–5.48 (m, HꢁC(4), HꢁC(5), HꢁC(8), HꢁC(9)); 4.05 (t, J¼6.7,
2 HꢁC(1); 1.98–2.09 (m, 2 HꢁC(3), 2 HꢁC(6), 2 HꢁC(7), 2 HꢁC(10)); 2.04 (s, MeCO); 1.68 (dt, J¼
14.1, 6.8, 2 HꢁC(2)); 1.23–1.37 (m, 2 HꢁC(11), 2 HꢁC(12), 2 HꢁC(13)); 0.88 (t, J¼7.0, 3 HꢁC(14)).
13C-NMR (125.8 MHz, CDCl3): 171.1; 130.9; 130.3; 129.0; 128.9; 64.0; 32.6; 31.5; 29.4; 28.8; 28.4; 27.23;
.
27.22; 22.6; 21.0; 14.1. MS (70 eV): 252 (0.2, Mþ ), 192 (6), 167 (0), 151 (1), 149 (2), 138 (3), 135 (10), 121
(13), 110 (7), 107 (4), 99 (1), 96 (2), 95 (5), 93 (5), 91 (1), 82 (16), 81 (100), 79 (14), 77 (1), 69 (19), 67
(13), 61 (1), 57 (3), 55 (19), 53 (4), 43 (34), 41 (22), 39 (5), 31 (0).
Field Tests. The synthetic compounds were dissolved in hexane (Merck, p.a.) and soaked from the
inside into the walls of red rubber tube dispensers (8ꢂ15 mm). Each lure was placed in an opaque white
delta trap (trapping window sides 10 cmꢂ11 cmꢂ10 cm and trap length 18 cm), which had an
exchangeable bottom (11 cmꢂ18 cm), coated with sticky material. (ꢂAtracon Aꢃ traps and Pestifix glue
were obtained from Flora Co., Tartu, Estonia). Tests were carried out at the edge of a private garden
˙
close to the small town Sasnava, Marijampole region (South Lithuania) from July 14 to August 3, 2006.
The private garden was bordering with a shelter belt where various deciduous trees and shrubs were
growing. Each trap was fixed on a branch of a fruit-tree ca. 2 m from the ground, and was inspected and
moved to the next trap location (within each replication) every 3 d. The distance between the traps was at
least 15 m. Five replicates of each compound listed in Table 1 were used. The moth specimens captured
were identified by analysis of their genitalia. Before the identification, the moths were rinsed from the
sticky glue in hexane. Representative specimens are kept in the insect collection at the Institute of
Ecology, Vilnius, Lithuania.
Statistical Analysis. Data from the field tests were transformed by the formula (nþ1)0.5, where n was
the number of moths captured per trap. The values thus obtained were analyzed by Duncanꢃs multiple
range test, and significantly different values were separated [63].
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Received June 13, 2008