New Synthetic Method for the Racemic form of the Bean Weevil Acanthoscelides obtectus Male Pheromone

Full text of DOI:10.1007/s10600-018-2429-5

DOI 10.1007/s10600-018-2429-5
Chemistry of Natural Compounds, Vol. 54, No. 3, May, 2018
NEW SYNTHETIC METHOD FOR THE RACEMIC
FORM OF THE BEAN WEEVIL Acanthoscelides obtectus
MALE PHEROMONE
1*
2
I. M. Sakhautdinov, A. M. Gumerov,
1
3
A. F. Mukhametꢀyanova, A. B. Atangulov,
1
and M. S. Yunusov
Many natural allenes and their derivatives showed cytotoxic, antibacterial, antiviral, fungicidal, and other activities [1, 2].
Herein, the synthesis of racemic pheromone methyl (R,E)-tetradeca-2,4,5-trienoate is reported.
H
H
7
CO Me
2
The pheromone methyl (R,E)-tetradeca-2,4,5-trienoate was isolated in 1970 by Horler [3] from male bean weevil
Acanthoscelides obtectus (Say). Now, several syntheses of this compound are known [1]. The allene motif was introduced in
the early synthesis steps in all previous studies [4–9]. This complicated the task because the allene was reactive. The method
proposed by us is distinctive because the allene motif is introduced in the last step using a Wittig reaction.
The racemic analog of 1 was synthesized in four steps starting with commercially available methyl-4-bromocrotonate
2 and decanoic acid 3 (Scheme 1).
HOOC
8
3
c
MeO C
2
_
+
Ph P
3
Br
Ph P
3
H
CO Me
2
Cl
d
a
b
+
CO Me
CO Me
2
2
O
Br
8
H
n-C H
8 17
2
4
6
5
1
a. PPh , C H ; b. KOH; c. SOCl , C H ; d. Et N, CH Cl , –10ꢂC
3
6
6
2
6
6
3
2
2
Scheme 1
Wittig olefination of unstabilized ylide 5 and the ketene produced in situ from decanoic acid and acid chloride 6
produced racemic bean weevil pheromone 1 in 35% yield calculated for starting acid 3.
(E)-(4-Methoxy-4-oxobut-2-enyl)triphenylphosphonium Bromide (4). A solution of methyl 4-bromocrotonate
(2, 1.8 g, 10 mmol) in anhydrous C H (10 mL) at room temperature was stirred, treated with triphenylphosphine (2.9 g,
6
6
11 mmol) dissolved in C H (3 mL), and stirred for 3 h. The resulting phosphonium salt was filtered off and rinsed several
6
6
–1
times with hot C H . Yield 4.4 g (99%), white powder, mp 121°C, IR-spectrum (ꢁ, cm ): 1567, 1629, 1715. C H O P.
6
6
23 21 2
Methyl (2E)-4-(Triphenylphosphoranylidene)but-2-enoate (5). Salt 4 (1 g, 2.3 mmol) was dissolved in H O
2
(45 mL) at room temperature, treated with KOH until basic (pH 9), and stirred for 15 min. The resulting precipitate was
filtered off, rinsed with H O, dissolved in CH Cl , and dried over K CO . Yield 0.8 g (98%), orange powder, mp 73°C,
2
2
2
2
3
–1
IR spectrum (ꢁ, cm ): 1577, 1626, 1723.
1) Ufa Institute of Chemistry, Russian Academy of Sciences, 69 Prosp. Oktyabrya, Ufa, Republic of Bashkortostan,
450054, Russia, fax: (347) 235 60 66; e-mail: ioh039@mail.ru; 2) Ufa State Petroleum Technical University, 1 Kosmonavtov
St., Ufa, 450062, e-mail: info@rusoil.net; 3) Bashkir State University, 32 Zaki Validi St., Ufa, 450076, e-mail: afmhim@bk.ru.
Translated from Khimiya Prirodnykh Soedinenii, No. 3, May–June, 2018, pp. 526–527. Original article submitted October 23, 2017.
©
622
0009-3130/18/5403-0622 2018 Springer Science+Business Media, LLC

Preparation of ( ) Methyl 2,4,5-Tetradecatrienoate (1). Asolution of decanoic acid (3, 1 g, 5.8 mmol) in anhydrous
C H (10 mL) was treated with a five-fold excess of thionyl chloride and refluxed for 3 h. The solvent and excess of thionyl
6
6
chloride were removed in a rotary evaporator. The resulting acid chloride was used without further purification and was added
dropwise to a cold (–10°C) solution of methyl (2E)-4-(triphenylphosphoranylidene)but-2-enoate (5, 2 g, 5.8 mmol) and Et N
3
(0.8 mL, 5.8 mmol) in CH Cl . The mixture was stirred for 0.5 h. The solvent was distilled off. The products were separated
2
2
by flash chromatography over silica gel (CH Cl eluent). Spectral data of synthesized 1 were identical to those in the literature
2
2
[3, 9]. The product was unstable with a half-life of 10 h at room temperature and could be stored for a long time in n-hexane
at –13°C [3].
Thus, a convenient method for synthesizing the male pheromone of bean weevil A. obtectus, methyl (R,E)-tetradeca-
2,4,5-trienoate from commercially available methyl-4-bromocrotonate and decanoic acid was proposed by us.
ACKNOWLEDGMENT
The work was performed according to a research plan for Ufa Institute of Chemistry, RAS, on the topic “Synthesis of
Biologically Active Heterocyclic and Terpenoid Compounds” (State Reg. No. AAAA-A17-117011910025-6). Information
support came from RFBR Grant 13-00-14056. Spectral studies were performed on equipment at the Khimiya CUC, UfIC,
RAS.
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