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7-Vinyldecyl acetate, novel inhibitor of pheromonal attraction in the false codling moth, cryptophlebia leucotreta
00404039/90$3.00+ .OO PcrgamonPressplc
Tcmhedron Ltums. Vo1.31.No.40. pp 5771-57721990 Ritcd in Gmu Britain
7-VINVLDECVL
ACETATE,
NOVEL INHIBITOR OF PBEROMONAL
TEE FALSE CODLINQ MOTE,CRYPT0PHLBBIA
ATTRACTION
IN
LBUCOTRBTA
B.V. Burger*a, M. le Roux”, W .M. Mackenrothaeb, H.S.C. Spice” and J.H. Hofmeyrc a Laboratory for Ecological
Chemhy, Univereity of Stellenboach, Stellenboech 7600, R.S.A.
b Preeent addreae: BASF Aktidhaft ’ S.A. Co-op.
D6700
Ludnilplhafen,
Citrue Exchange, P.O. Box 212, Citruedal7346,
F.R.C.
R.S.A.
It wan found that 7-vinyldecyl acetate, a by-product of the lynthaie of one of the conetituentr of w: the eex attractent of the falee cod@ moth, CrpptopAMia /erotreto, effectively dierupte the attraction of mde mothe to virgin femdee or to eynthetx luree. Femdee
of the falee codling moth, Cryploplrlebio leucotreta, emit a rex pheromone
conepacific mdee and hao been identified to con&t
of (E)- and (Z)-&dodecenyl
which
attract6
acetate in a 1:l ratio’.
Other
ratioe and the preeence of dodecyl acetate in the recretion have eubeequently been reported, end eynthetic lures containing
the two uneaturated
teab24.
The erratic rwulte
acetatea in widely that
varying
are often obtained
contributed
to euetoin continuing
formylation
of “competing” synthetic lures. was, for example,
mdemin field
were found to attract
commacid
intereet in the eompoeition
fdee
codling
of the eex pheromone
WM ueed, a wide variation
found in po ulatione from different geographicd 1
moth
luree possibly
of the insect and in the
In a rtudy in which aolventlem introduction
glande of the ineect into the injector of a glu chromatograph two acetates
proportione
with
of the sex pheromone in the proportion of the
origine, while reverd
other
compound6 were deo identified in the glande.
In an evduation found that, dthough contained
of this materid
in a concentration
of approximatdy
acetate
concentration
of 4.5%.
(E)-&dodecenyl
synthetic
fdee codling moth lurca, formulatione
acetate wee ueed, did not attract any mde mothe.
the major constituent
an impurity
(Z)-&lodecenyl
formulated
of diierently
certain batch of (E)-&dodecenyl
were wed
had the correct rtructure, 9%.
in a ratio of 1:l would
The impurity
had a rlightly
acetate or itr Z-ieomer.
analyeie of the mixture, (E)-&dodecenyl
therefore
thi
formulation
batch of the eeber in which (E)-
and
the impurity
in a
have contained
CJC retention
shorter
From a comparison
A typicd
of meee rpectrd
in which a
On clmer inepection it orea
time on en apolar phaee than data obtained
acetate and the impurity appeared to be structurdly
by QC/HR-MS related, the only
difference between the maee rpectra of the two compounde being the higher relative abundance of the
significent
ions at “/r, 123 end 137, and the lower abundance of the ion at m/e 166 in the rpectrum of the impurity’. theee differences could not be trenelated unequivocdly by preparative multiplicities 7-vinyldecyl (E)-2-hexenyl impurity
CC for NMR epectrd determined acetate
by the
In the preparation
1.
Data obtained
technique,
furnished
of (E)-&lodecenyl
from the ‘II and “C conclusive
evidence
that
Since
WM isolated
NMR rpectra’l, and the
impurity
acetate 6 by a catdyet-induced
wee
coupling of
acetate 2 with the Crignard
reegent 3, as shown in the following scheme, the branched-chain 1 ie formed by attack at the vinylogoue position with a concurrent shift of the double bond 6,9
The ratio in which the ieomeric changing
analysis.
APT
into an acceptable etructure, the impurity
the reaction
branched-chain
conditions.
compound
esters 1 and 6 are formed, can be controlled,
Th e f o 11owing
procedure
gave
a find
product
to a certain containing
1. The Qrignard reagent 3, prepared from 1-Cbutoxy-6-chlorohexane
5771
extent, by 2~?% of the
5772
4
5 1) Ii’ 2) Ae,O/NEt 3
I
-0Ae
+ 6 10
1
(96.3 g, 0.6 md) and Mg tumingr (13.3 g, 0.55 mol) in THF (100 ml), WM added drop&e acetate 2 (Ml.9 g, 0.41 mol) Md the catelyrt,
of (E)-2-hexenyl
LiCl (0.9 g, 0.02 mol) in THF (46 ml). ice wm added.
the reection mixture at 70°C for a further 15 h, crushed
The organic product, belated
in the ueual manner, contained the etraight- and branched-ehein 28 (GC andyain). Removal of the protective group 10 and acetylstion” gave
: acetatea6 and 1 in thm eame ratio and in an overdl yield of 60%. Tha branched-chain
iwmere 4 and 5 in I) ratio of 72 the
After &ring
by careful fractionation
An dready eynthetic
and preparative
mentioned,
fdxe codling
compound
The drong
in experimenb
wee determined.
inhibition
It wae, for inetxnce,
femdee
plus polyethylene
femdee
were expoeed in amdl wire gue
femdee
every 3-4
daya.
cap dixpennem containing
Although
strong pheromond
found
of andoguee,
Thme results furthermore
preeence of dmilarly
formed branched&sin
expected behaviourd
response in the target inxecb.
in C. leucotreto
of live virgin femdee
centrally
acetate 1. In theno experiments
the inhibitory
etc., it ie clear that 7-vinyldecyl
and might find application
threshold acetate
in controlling
in other eynthetic
pheromonea
REPEBENC%I AND NOTES
(., CA&C); 1.1-1.55 (m, CBa, 14 H); 0.93 (t, CBa, J = 5.9 Es). “C NMR (%I Mtls, 34’C, benswd5 at 6 123.0 wan wed I internd reference and lock solvent in 1.7 mm O.D. umple Lube). SC: 169.80 (a, Co);
in UK 8 August
1WO)
of thir
actr en a
this inaect peat the powible
that do not elicit the
1. C.J. Penaona P.J. Flitter, and W.J. Nooyen 1. Chem. Ed 3,717 (1977 0. A. An&d, 0. Dacoiru 1. Lha&, J.-P. T&au, and P. Z@ti, Cot Fi 1. ‘I’ro YJ, 259 (1981). C. Droiru, and M. Calloia. A aomie $76 &MS). 3. P. Zag&i, B. Ldume-C&u Ap 56 SS(W84). 4. D.R. .I1 P.S. Beew A. Car B.P. N-bitt andE.A.S. La && Eniomol E 2. tiwfirrd.fc, 1fl7 (i985). 5. A.B. A&+, I. S&u., 0 5 C&W&, &d E.J. B&w. 6. EMS: m s 166 (2, GrBr ), 137 (34. CwBtr 123 (35. ctats.), 109 (10, C&a), Q5 (30, C&), ~(52, CaB,). 67 (53, c h l), 61 (13), 55 tQ4,. 43 (lag, 41 1’64). 7. ‘B NMR (80 MHs, Jo”C, bensmw-d5 at 6 7.20 wu used I internal reference in 1.7 mm O.D. #ampletubs). 6B: 5.521 (m, IiA, JAB = 10.12 Hr, JAc = 17.21 Es, JAD = 3.53 Es); 6.035 (m. JIB, JBc = 2.13 An, J BD = -0.27 Es); 6.005 (m, EC, JCD = -0.59 Es); 4.02 (t, OCBz, J = 6.4 As); 1.95 (m, I$,); 1.74
(Received
for
in tube trapa nnd were replaced with fresh
mggeat that it might be advirable to invextigate
by-producta
of
by thin
that whereee 370 mdea were caught over a
further research is needed to determine
the activity
reepome
not a xingle moth wee caught in trapa baited with
2 pll of the branched-chain
cnges suspended
inhibitor in Crpptop&k&ia kucotrcfa
by mating disruption.
acetate 1 strongly reduced the nttractivenexa of pheromond
in which ib effect on the attractiveness
period of 21 daya in trape, each baited with a virgin femde,
itr mode of action,
ieomer I wu ieolrted
QC.
the preeence of the branched-shain
moth lures
wzm duo illuetrated
mdea of the epecia
compound,
d 70% to a mixture
prepared by adding CuBr (2.9 g, 0.02 mol) to
Tcmhedron Ltums. Vo1.31.No.40. pp 5771-57721990 Ritcd in Gmu Britain
7-VINVLDECVL
ACETATE,
NOVEL INHIBITOR OF PBEROMONAL
TEE FALSE CODLINQ MOTE,CRYPT0PHLBBIA
ATTRACTION
IN
LBUCOTRBTA
B.V. Burger*a, M. le Roux”, W .M. Mackenrothaeb, H.S.C. Spice” and J.H. Hofmeyrc a Laboratory for Ecological
Chemhy, Univereity of Stellenboach, Stellenboech 7600, R.S.A.
b Preeent addreae: BASF Aktidhaft ’ S.A. Co-op.
D6700
Ludnilplhafen,
Citrue Exchange, P.O. Box 212, Citruedal7346,
F.R.C.
R.S.A.
It wan found that 7-vinyldecyl acetate, a by-product of the lynthaie of one of the conetituentr of w: the eex attractent of the falee cod@ moth, CrpptopAMia /erotreto, effectively dierupte the attraction of mde mothe to virgin femdee or to eynthetx luree. Femdee
of the falee codling moth, Cryploplrlebio leucotreta, emit a rex pheromone
conepacific mdee and hao been identified to con&t
of (E)- and (Z)-&dodecenyl
which
attract6
acetate in a 1:l ratio’.
Other
ratioe and the preeence of dodecyl acetate in the recretion have eubeequently been reported, end eynthetic lures containing
the two uneaturated
teab24.
The erratic rwulte
acetatea in widely that
varying
are often obtained
contributed
to euetoin continuing
formylation
of “competing” synthetic lures. was, for example,
mdemin field
were found to attract
commacid
intereet in the eompoeition
fdee
codling
of the eex pheromone
WM ueed, a wide variation
found in po ulatione from different geographicd 1
moth
luree possibly
of the insect and in the
In a rtudy in which aolventlem introduction
glande of the ineect into the injector of a glu chromatograph two acetates
proportione
with
of the sex pheromone in the proportion of the
origine, while reverd
other
compound6 were deo identified in the glande.
In an evduation found that, dthough contained
of this materid
in a concentration
of approximatdy
acetate
concentration
of 4.5%.
(E)-&dodecenyl
synthetic
fdee codling moth lurca, formulatione
acetate wee ueed, did not attract any mde mothe.
the major constituent
an impurity
(Z)-&lodecenyl
formulated
of diierently
certain batch of (E)-&dodecenyl
were wed
had the correct rtructure, 9%.
in a ratio of 1:l would
The impurity
had a rlightly
acetate or itr Z-ieomer.
analyeie of the mixture, (E)-&dodecenyl
therefore
thi
formulation
batch of the eeber in which (E)-
and
the impurity
in a
have contained
CJC retention
shorter
From a comparison
A typicd
of meee rpectrd
in which a
On clmer inepection it orea
time on en apolar phaee than data obtained
acetate and the impurity appeared to be structurdly
by QC/HR-MS related, the only
difference between the maee rpectra of the two compounde being the higher relative abundance of the
significent
ions at “/r, 123 end 137, and the lower abundance of the ion at m/e 166 in the rpectrum of the impurity’. theee differences could not be trenelated unequivocdly by preparative multiplicities 7-vinyldecyl (E)-2-hexenyl impurity
CC for NMR epectrd determined acetate
by the
In the preparation
1.
Data obtained
technique,
furnished
of (E)-&lodecenyl
from the ‘II and “C conclusive
evidence
that
Since
WM isolated
NMR rpectra’l, and the
impurity
acetate 6 by a catdyet-induced
wee
coupling of
acetate 2 with the Crignard
reegent 3, as shown in the following scheme, the branched-chain 1 ie formed by attack at the vinylogoue position with a concurrent shift of the double bond 6,9
The ratio in which the ieomeric changing
analysis.
APT
into an acceptable etructure, the impurity
the reaction
branched-chain
conditions.
compound
esters 1 and 6 are formed, can be controlled,
Th e f o 11owing
procedure
gave
a find
product
to a certain containing
1. The Qrignard reagent 3, prepared from 1-Cbutoxy-6-chlorohexane
5771
extent, by 2~?% of the
5772
4
5 1) Ii’ 2) Ae,O/NEt 3
I
-0Ae
+ 6 10
1
(96.3 g, 0.6 md) and Mg tumingr (13.3 g, 0.55 mol) in THF (100 ml), WM added drop&e acetate 2 (Ml.9 g, 0.41 mol) Md the catelyrt,
of (E)-2-hexenyl
LiCl (0.9 g, 0.02 mol) in THF (46 ml). ice wm added.
the reection mixture at 70°C for a further 15 h, crushed
The organic product, belated
in the ueual manner, contained the etraight- and branched-ehein 28 (GC andyain). Removal of the protective group 10 and acetylstion” gave
: acetatea6 and 1 in thm eame ratio and in an overdl yield of 60%. Tha branched-chain
iwmere 4 and 5 in I) ratio of 72 the
After &ring
by careful fractionation
An dready eynthetic
and preparative
mentioned,
fdxe codling
compound
The drong
in experimenb
wee determined.
inhibition
It wae, for inetxnce,
femdee
plus polyethylene
femdee
were expoeed in amdl wire gue
femdee
every 3-4
daya.
cap dixpennem containing
Although
strong pheromond
found
of andoguee,
Thme results furthermore
preeence of dmilarly
formed branched&sin
expected behaviourd
response in the target inxecb.
in C. leucotreto
of live virgin femdee
centrally
acetate 1. In theno experiments
the inhibitory
etc., it ie clear that 7-vinyldecyl
and might find application
threshold acetate
in controlling
in other eynthetic
pheromonea
REPEBENC%I AND NOTES
(., CA&C); 1.1-1.55 (m, CBa, 14 H); 0.93 (t, CBa, J = 5.9 Es). “C NMR (%I Mtls, 34’C, benswd5 at 6 123.0 wan wed I internd reference and lock solvent in 1.7 mm O.D. umple Lube). SC: 169.80 (a, Co);
in UK 8 August
1WO)
of thir
actr en a
this inaect peat the powible
that do not elicit the
1. C.J. Penaona P.J. Flitter, and W.J. Nooyen 1. Chem. Ed 3,717 (1977 0. A. An&d, 0. Dacoiru 1. Lha&, J.-P. T&au, and P. Z@ti, Cot Fi 1. ‘I’ro YJ, 259 (1981). C. Droiru, and M. Calloia. A aomie $76 &MS). 3. P. Zag&i, B. Ldume-C&u Ap 56 SS(W84). 4. D.R. .I1 P.S. Beew A. Car B.P. N-bitt andE.A.S. La && Eniomol E 2. tiwfirrd.fc, 1fl7 (i985). 5. A.B. A&+, I. S&u., 0 5 C&W&, &d E.J. B&w. 6. EMS: m s 166 (2, GrBr ), 137 (34. CwBtr 123 (35. ctats.), 109 (10, C&a), Q5 (30, C&), ~(52, CaB,). 67 (53, c h l), 61 (13), 55 tQ4,. 43 (lag, 41 1’64). 7. ‘B NMR (80 MHs, Jo”C, bensmw-d5 at 6 7.20 wu used I internal reference in 1.7 mm O.D. #ampletubs). 6B: 5.521 (m, IiA, JAB = 10.12 Hr, JAc = 17.21 Es, JAD = 3.53 Es); 6.035 (m. JIB, JBc = 2.13 An, J BD = -0.27 Es); 6.005 (m, EC, JCD = -0.59 Es); 4.02 (t, OCBz, J = 6.4 As); 1.95 (m, I$,); 1.74
(Received
for
in tube trapa nnd were replaced with fresh
mggeat that it might be advirable to invextigate
by-producta
of
by thin
that whereee 370 mdea were caught over a
further research is needed to determine
the activity
reepome
not a xingle moth wee caught in trapa baited with
2 pll of the branched-chain
cnges suspended
inhibitor in Crpptop&k&ia kucotrcfa
by mating disruption.
acetate 1 strongly reduced the nttractivenexa of pheromond
in which ib effect on the attractiveness
period of 21 daya in trape, each baited with a virgin femde,
itr mode of action,
ieomer I wu ieolrted
QC.
the preeence of the branched-shain
moth lures
wzm duo illuetrated
mdea of the epecia
compound,
d 70% to a mixture
prepared by adding CuBr (2.9 g, 0.02 mol) to