U.S. patent application number 14/189220 was filed with the patent office on 2014-09-18 for (z,z,e)-1-chloro-6,10,12-pentadecatriene and method for preparing (z,z,e)-7,11,13-hexadecatrienal by using same.
This patent application is currently assigned to Shin-Etsu Chemical Co., Ltd.. The applicant listed for this patent is Shin-Etsu Chemical Co., Ltd.. Invention is credited to Takehiko Fukumoto, Naoki Ishibashi, Yuki Miyake, Miyoshi Yamashita.
Application Number | 20140275656 14/189220 |
Document ID | / |
Family ID | 51418929 |
Filed Date | 2014-09-18 |
United States Patent
Application |
20140275656 |
Kind Code |
A1 |
Miyake; Yuki ; et
al. |
September 18, 2014 |
(Z,Z,E)-1-CHLORO-6,10,12-PENTADECATRIENE AND METHOD FOR PREPARING
(Z,Z,E)-7,11,13-HEXADECATRIENAL BY USING SAME
Abstract
Provided are (Z,Z,E)-1-chloro-6,10,12-pentadecatriene that can
be synthesized without an oxidation reaction and a method for
preparing (Z,Z,E)-7,11,13-hexadecatienal by using
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene while not using an
oxidation reaction. More specifically, provided is a method for
preparing (Z,Z,E)-7,11,13-hexadecatrienal including a step of
reacting a Grignard reagent into which
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene is converted with ethyl
orthoformate to obtain (Z,Z,E)-1,1-diethoxy-7,11,13-hexadecatriene,
and a step of treating the
(Z,Z,E)-1,1-diethoxy-7,11,13-hexadecatriene with an acid to obtain
(Z,Z,E)-7,11,13-hexadecatrienal.
Inventors: |
Miyake; Yuki; (Joetsu-shi,
JP) ; Yamashita; Miyoshi; (Joetsu-shi, JP) ;
Fukumoto; Takehiko; (Joetsu-shi, JP) ; Ishibashi;
Naoki; (Joetsu-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Shin-Etsu Chemical Co., Ltd. |
Tokyo |
|
JP |
|
|
Assignee: |
Shin-Etsu Chemical Co.,
Ltd.
Tokyo
JP
|
Family ID: |
51418929 |
Appl. No.: |
14/189220 |
Filed: |
February 25, 2014 |
Current U.S.
Class: |
570/189 ;
570/257 |
Current CPC
Class: |
C07C 17/2632 20130101;
C07C 17/16 20130101; C07C 21/215 20130101; C07C 41/50 20130101;
C07C 45/515 20130101; C07C 17/16 20130101; C07C 21/215 20130101;
C07C 17/2632 20130101; C07C 21/215 20130101; C07C 41/50 20130101;
C07C 43/303 20130101; C07C 45/515 20130101; C07C 47/21
20130101 |
Class at
Publication: |
570/189 ;
570/257 |
International
Class: |
C07C 21/215 20060101
C07C021/215; C07C 17/26 20060101 C07C017/26 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 14, 2013 |
JP |
2013-051711 |
Claims
1. (Z,Z,E)-1-Chloro-6,10,12-pentadecatiene.
2. A method for preparing (Z,Z,E)-1-chloro-6,10,12-pentadecatriene,
comprising: a step of chlorinating (Z,Z,E)-3,7,9-dodecatrien-1-01
into (Z,Z,E)-1-chloro-3,7,9-dodecatriene, and a step of reacting a
Grignard reagent into which the (Z,Z,E)-1-chloro-3,7,9-dodecatriene
is converted with 1-bromo-3-chloropropane.
3. A method for preparing (Z,Z,E)-7,11,13-hexadecatrienal,
comprising: a step of reacting a Grignard reagent into which
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene is converted with ethyl
orthoformate to obtain (Z,Z,E)-1,1-diethoxy-7,11,13-hexadecatriene,
and a step of treating the
(Z,Z,E)-1,1-diethoxy-7,11,13-hexadecatriene with an acid to obtain
(Z,Z,E)-7,11,13-hexadecatrienal.
Description
RELATED APPLICATION
[0001] This application claims priority from Japanese Patent
Application No. 2013-051711, filed Mar. 14, 2013, the disclosure of
which is incorporated by reference herein in its entirety.
FIELD AND BACKGROUND OF THE INVENTION
[0002] The present invention relates to a method for preparing
(Z,Z,E)-7,11,13-hexadecatrienal, which is a sex pheromone substance
of the citrus leafminer, a pest of citrus, by using
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene.
[0003] The citrus leafminer (Phyllocnistis citrella) is an
important pest of citrus. It is parasitic and causes damage in
young leaves and thereby has a serious influence on the growth of
nursery trees. Its feeding damage marks accelerate occurrence of
citrus canker. This pest mines the undersurface of leaves so that
it cannot be controlled easily by pesticides. Its resistance to
pesticides is also observed. Biological control methods have
therefore been attracting attentions and a method of using a sex
pheromone substance is expected as one of them.
[0004] It has been identified (W. S. Leal et al., J. Chem. Ecol.
32(1), 155-168(2006)) that the sex pheromone composition of the
citrus leafminer contains (Z,Z,E)-7,11,13-hexadecatrienal,
(Z,Z)-7,11-hexadecadienal, and (Z)-7-hexadecenal as the main
component, the second component, and the third component,
respectively. Further, a 3:1 mixture of
(Z,Z,E)-7,11,13-hexadecatrienal and (Z,Z)-7,11-hexadecadienal has
been shown to have higher attractiveness than the main component
alone (W. S. Leal et al., J. Chem. Ecol. 32(1), 155-168(2006) and
T. Ando et al., J. Pestic. Sci., 33(2), 152-158(2008)).
[0005] Several preparation methods for synthesizing the sex
pheromone substance (Z,Z,E)-7,11,13-hexadecatrienal have been
reported. For example, it has been reported (W. S. Leal et al., J.
Chem. Ecol. 32(1), 155-168(2006)) that the sex pheromone substance
can be obtained through a Wittig reaction between
10-(1,3-dioxan-2-yl)-(Z)-4-decenal and
(Z)-2-pentenyltriphenylphosphonium bromide, followed by
deprotection of acetal. It has also been reported (T. Ando et al.,
J. Pestic. Sci., 33(2), 152-158(2008) and J. G. Millar et al., J.
Chem. Ecol., 32(1), 169-194(2006)) that the sex pheromone substance
can be obtained through oxidation of
(Z,Z,E)-7,11,13-hexadecatrienol with pyridinium chlorochromate and
then separation of an isomer at 11-position by the subsequent
purification with a silver nitrate column.
SUMMARY OF THE INVENTION
[0006] Any of the preparation methods thus reported, however, uses
an oxidation reaction as a key reaction. The oxidation reaction
often involves a risk of explosion or the like, and in an
industrial scale, it has difficulty in isolating an aldehyde, which
is a reaction product, with high purity and high yield.
[0007] With the foregoing in view, the present invention has been
made. An object of the invention is to provide
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene that can be synthesized
without an oxidation reaction and a method for preparing
(Z,Z,E)-7,11,13-hexadecatrienal by using the
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene, the method therefore not
comprising a step of an oxidation reaction.
[0008] In the invention, it has been found that
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene can be mass-produced at a
low cost, and (Z,Z,E)-7,11,13-hexadecatrienal can be obtained with
high purity and at high yield by converting the
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene into a corresponding
Grignard reagent, conducting a coupling reaction between the
Grignard reagent and ethyl orthoformate, and then conducting a
hydrolysis treatment, leading to the completion of the
invention.
[0009] In one aspect of the invention, there is provided
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene. In another aspect of the
invention, there is also provided a method for preparing
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene comprising a step of
chlorinating (Z,Z,E)-3,7,9-dodecatrien-1-ol into
(Z,Z,E)-1-chloro-3,7,9-dodecatriene and a step of reacting a
Grignard reagent into which the (Z,Z,E)-1-chloro-3,7,9-dodecatriene
is converted with 1-bromo-3-chloropropane. In a further aspect of
the invention, there is also provided a method for preparing
(Z,Z,E)-7,11,13-hexadecatrienal comprising a step of reacting a
Grignard reagent into which
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene is converted with ethyl
orthoformate to obtain (Z,Z,E)-1,1-diethoxy-7,11,13-hexadecatriene,
and a step of treating the
(Z,Z,E)-1,1-diethoxy-7,11,13-hexadecatriene with an acid to obtain
(Z,Z,E)-7,11,13-hexadecatrienal.
[0010] According to the invention, none of the steps require an
oxidation reaction so that (Z,Z,E)-7,11,13-hexadecatrienal can be
mass-produced at a low cost with high reliability.
[0011] Moreover, according to the invention,
(Z,Z,E)-7,11,13-hexadecatrienal can be prepared efficiently by
coupling the Grignard reagent obtained from
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene with ethyl
orthoformate.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0012] The present invention now will be described more fully
hereinafter in which embodiments of the invention are provided with
reference to the accompanying drawings. This invention may,
however, be embodied in many different forms and should not be
construed as limited to the embodiments set forth herein; rather,
these embodiments are provided so that this disclosure will be
thorough and complete, and will fully convey the scope of the
invention to those skilled in the art.
[0013] The terminology used in the description of the invention
herein is for the purpose of describing particular embodiments only
and is not intended to be limiting of the invention. As used in the
description of the invention and the appended claims, the singular
forms "a", "an" and "the" are intended to include the plural forms
as well, unless the context clearly indicates otherwise. Unless
otherwise defined, all technical and scientific terms used herein
have the same meaning as commonly understood by one of ordinary
skill in the art to which this invention belongs. All references
cited are incorporated herein by reference in their entirety.
[0014] (Z,Z,E)-1-Chloro-6,10,12-pentadecatriene (3) can be
prepared, for example, by chlorination of
(Z,Z,E)-3,7,9-dodecatrien-1-ol (1), a subsequent conversion of the
resulting product into a corresponding Grignard reagent, and a
reaction of the Grignard reagent with 1-bromo-3-chloropropane.
[0015] The (Z,Z,E)-3,7,9-dodecatrien-1-ol (1), a starting material,
can be prepared, for example, by a Wittig reaction between an ylide
derived from 5-chloro-1-pentyne and 2-pentenal, an addition of
carbon or carbons to the terminal alkyne, and hydrogenation of the
triple bond. The hydrogenation of the carbon-carbon triple bond
into a carbon-carbon double bond can be achieved using a known
catalyst, for example, a P2-nickel catalyst.
##STR00001##
[0016] The (Z,Z,E)-3,7,9-dodecatrien-1-ol (1) thus obtained can be
reacted with a chlorinating agent to produce
(Z,Z,E)-1-chloro-3,7,9-dodecatriene (2). This chlorination reaction
can be conducted, for example, by reacting the
(Z,Z,E)-3,7,9-dodecatrien-1-ol (1) with a chlorinating agent in a
solvent in the presence of a base.
##STR00002##
[0017] Examples of the chlorinating agent include thionyl chloride,
sulfuryl chloride, methanesulfonyl chloride, p-toluenesulfonyl
chloride, benzenesulfonyl chloride, phosphorus trichloride, and
phosphorus pentachloride. Methanesulfonyl chloride is preferred
from the standpoint of isomerization. The chlorinating agent can be
used in an amount of preferably from 1.0 to 1.6 mol per mol of the
(Z,Z,E)-3,7,9-dodecatrien-1-ol (1). When the amount is less than
1.0 mol, the reaction may not proceed smoothly. When the amount is
more than 1.6 mol, some of the chlorinating agent may be
wasted.
[0018] Examples of the base to be used for the chlorination
reaction include pyridine-based compounds or pyridines such as
pyridine and collidine; alkylamine compounds such as triethylamine,
tributylamine and N,N-diisopropylethylamine; and aniline compounds
such as aniline and N,N-diethylaniline. Pyridine is preferred from
the standpoint of reactivity. The base can be used in an amount of
preferably from 1.0 to 2.2 mol per mol of the
(Z,Z,E)-3,7,9-dodecatrien-1-ol (1). When the amount is less than
1.0 mol, the reaction may not proceed smoothly. When the amount is
more than 2.2 mol, some of the base may be wasted.
[0019] Examples of the solvent to be used for the chlorination
reaction include hydrocarbon-based solvents such as toluene and
hexane; ether-based solvents such as tetrahydrofuran and diethyl
ether; and polar solvents such as N,N-dimethylformamide,
N,N-dimethylacetamide and dichloromethane. N,N-dimethylformamide is
preferred from the standpoint of reactivity. The solvent is used in
an amount of preferably from 50 to 500 g per mol of the
(Z,Z,E)-3,7,9-dodecatrien-1-ol (1). When the amount is less than 50
g, the reaction may not proceed smoothly. When the amount is more
than 500 g, some of the solvent may be wasted, and an amount of the
reactants may have to be reduced.
[0020] The reaction temperature to be used for the chlorination
reaction is preferably from 5 to 70.degree. C. When the temperature
is less than 5.degree. C., the reaction may not be completed. When
the temperature is more than 70.degree. C., the amount of an
impurity may increase.
[0021] The (Z,Z,E)-1-chloro-3,7,9-dodecatriene (2) is converted
into a corresponding Grignard reagent and then the Grignard reagent
is reacted with 1-bromo-3-chloropropane to obtain
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene (3).
##STR00003##
[0022] The Grignard reagent can be prepared by reacting the
(Z,Z,E)-1-chloro-3,7,9-dodecatriene (2) with magnesium in a
solvent.
[0023] Examples of the solvent include hydrocarbon-based solvents
such as toluene and hexane, and ether-based solvents such as
tetrahydrofuran and diethyl ether. Tetrahydrofuran is preferred
from the standpoint of a reaction rate for producing the Grignard
reagent. The solvent can be used in an amount of preferably from
200 to 450 g per mol of the (Z,Z,E)-1-chloro-3,7,9-dodecatriene
(2).
[0024] Magnesium can be used in an amount of preferably from 1.0 to
1.5 mol per mol of the (Z,Z,E)-1-chloro-3,7,9-dodecatriene (2).
[0025] Examples of the catalyst to be used for the coupling
reaction with the Grignard reagent include copper halides such as
cuprous chloride, cupric chloride, cuprous bromide, cupric bromide,
cuprous iodide and cupric iodide. Cuprous iodide is preferred from
the standpoint of reactivity. The catalyst can be used in an amount
of preferably from 0.003 to 0.03 mol per mol of the
(Z,Z,E)-1-chloro-3,7,9-dodecatriene (2).
[0026] The catalyst to be used for the coupling reaction with the
Grignard reagent is preferably used together with a cocatalyst.
Examples of the cocatalyst include phosphorus compounds such as
triethyl phosphite and triphenylphosphine. Triethyl phosphite is
preferred from the standpoint of reactivity. The cocatalyst can be
used in an amount of preferably from 0.001 to 0.05 mol per mol of
the (Z,Z,E)-1-chloro-3,7,9-dodecatriene (2).
[0027] Examples of the solvent to be used for the coupling reaction
with the Grignard reagent include hydrocarbon-based solvents such
as toluene and hexane, and ether-based solvents such as
tetrahydrofuran and diethyl ether. Tetrahydrofuran is preferred
from the standpoint of reactivity. The solvent can be used in an
amount of preferably from 50 to 300 g per mol of the
(Z,Z,E)-1-chloro-3,7,9-dodecatriene (2).
[0028] The reaction temperature to be used for the coupling
reaction with the Grignard reagent is preferably from 0 to
30.degree. C. When the reaction temperature is less than 0.degree.
C., the reaction may not proceed smoothly. When the reaction
temperature is more than 30.degree. C., a side reaction may take
place.
[0029] Next, a method for preparing (Z,Z,E)-7,11,13-hexadecatrienal
(5) by using the (Z,Z,E)-1-chloro-6,10,12-pentadecatriene(3) thus
obtained will be described.
[0030] First, the (Z,Z,E)-1-chloro-6,10,12-pentadecatriene(3) is
converted into a corresponding Grignard reagent, and then subjected
to the reaction with ethyl orthoformate to produce
(Z,Z,E)-1,1-diethoxy-7,11,13-hexadecatriene (4).
##STR00004##
[0031] The Grignard reagent can be prepared by reacting the
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene (3) with magnesium in a
solvent.
[0032] Examples of the solvent include hydrocarbon-based solvents
such as toluene and hexane, and ether-based solvents such as
tetrahydrofuran and diethyl ether. Tetrahydrofuran is preferred
from the standpoint of a reaction rate for producing the Grignard
reagent. The solvent can be used in an amount of preferably from
200 to 450 g per mol of the
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene (3).
[0033] Magnesium can be used in an amount of preferably from 1 to
1.5 mol per mol of the (Z,Z,E)-1-chloro-6,10,12-pentadecatriene
(3).
[0034] Examples of the solvent to be used for the coupling reaction
with the Grignard reagent include hydrocarbon-based solvents such
as toluene and hexane, and ether-based solvents such as
tetrahydrofuran and diethyl ether. A mixed solvent of
tetrahydrofuran and toluene is preferred from the standpoint of
reactivity. The solvent can be used in an amount of preferably from
100 to 800 g per mol of the
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene (3).
[0035] The reaction temperature to be used for the coupling
reaction with the Grignard reagent is preferably from 75 to
115.degree. C. When the reaction temperature is less than
75.degree. C., the reaction may not proceed smoothly. When the
reaction temperature is more than 115.degree. C., the solvent may
evaporate.
[0036] Finally, the (Z,Z,E)-1,1-diethoxy-7,11,13-hexadecatriene (4)
is treated with an acid to produce (Z,Z,E)-7,11,13-hexadecatrienal
(5). This reaction proceeds smoothly by distilling off ethanol,
which is a by-product, through a distillation column attached to a
reaction vessel, and no isomerization between E and Z isomers can
be found during the reaction. For example, the
(Z,Z,E)-1,1-diethoxy-7,11,13-hexadecatriene (4) is treated with an
acid in a solvent to hydrolyze the acetal group.
##STR00005##
[0037] Examples of the acid include inorganic acids such as
hydrochloric acid and hydrobromic acid, p-toluenesulfonic acid,
trifluoroacetic acid, acetic acid, iodotrimethylsilane, and
titanium tetrachloride. Hydrochloric acid is preferred from the
standpoint of reactivity.
[0038] The acid to be used in the above reaction has a
concentration of preferably from 5 to 50% by weight, more
preferably from 10 to 37% by weight. When the concentration is less
than 5% by weight, the reaction may not proceed smoothly. When the
concentration is more than 50% by weight, severe control of
temperature, pressure and the like may be required at the time when
the acid is used.
[0039] When, for example, 10% by weight hydrochloric acid is used
as the acid, its amount is preferably from 100 to 150 g per mol of
the (Z,Z,E)-1,1-diethoxy-7,11,13-hexadecatriene (4).
[0040] Examples of the solvent to be used for the acid treatment
include hydrocarbon-based solvents such as toluene and hexane;
various alcohol solvents such as methanol and ethanol; ether-based
solvents such as tetrahydrofuran and diethyl ether; and polar
solvents such as dichloromethane. Toluene is preferred from the
standpoint of reactivity. The solvent is used in an amount of
preferably 300 g or less per mol of the
(Z,Z,E)-1,1-diethoxy-7,11,13-hexadecatriene (4). When the amount is
more than 300 g, some of the solvent may be wasted and an amount of
the reactants may have to be reduced.
[0041] The reaction temperature to be used for the acid treatment
is preferably from 5 to 30.degree. C. When the reaction temperature
is less than 5.degree. C., the reaction may not proceed smoothly.
When the reaction temperature is more than 30.degree. C., the
amount of an impurity may increase.
EXAMPLES
[0042] The invention will hereinafter be described specifically by
Examples, but it is not limited to or by the Examples.
Example 1
Preparation of (Z,Z,E)-1-chloro-3,7,9-dodecatriene (2)
[0043] (Z,Z,E)-3,7,9-Dodecatrien-1-ol (169.47 g, 0.94 mol),
pyridine (134.2 g, 1.70 mol) and N,N-dimethylformamide (284 g) were
placed in a reaction vessel, and stirred at 5 to 10.degree. C. for
30 minutes. After stirring, methanesulfonyl chloride (151.2 g, 1.32
mol) was added dropwise thereto at 5 to 15.degree. C. After
completion of the dropwise addition, the reaction mixture was
stirred at 60 to 65.degree. C. for 2 hours. Then, water (471 g) was
added to the reaction mixture to terminate the reaction. Hexane
(471 g) was added thereto to separate the reaction mixture into
phases. The organic phase was washed with hydrochloric acid and
then with an aqueous sodium bicarbonate solution, and then
concentrated by removal of the solvent under reduced pressure. The
residue was distilled under reduced pressure to obtain
(Z,Z,E)-1-chloro-3,7,9-dodecatriene (bp: 114 to 120.degree. C./5
mmHg, 166.93 g, 0.84 mol) with a yield of 89.2%.
[0044] [Nuclear magnetic resonance spectrum].sup.1H-NMR (300 MHz,
CDCl.sub.3): .delta.1.02 (3H, t), 2.08-2.19 (4H, m), 2.25 (2H, dt),
2.52 (2H, dt), 3.51 (2H, t), 5.30 (1H, dt), 5.41 (1H, dt), 5.55
(1H, dt), 5.72 (1H, dt), 5.98 (1H, dd), 6.28 (1H, dd); .sup.13C-NMR
(75.6 MHz, CDCl.sub.3): .delta.13.57, 25.86, 27.49, 27.52, 30.70,
44.16, 124.47, 125.38, 128.69, 129.24, 132.26, 136.65
[0045] [Mass spectrum] EI-mass spectrum (70 eV): m/z 198(M.sup.+),
95, 79, 67, 55, 41, 27
[0046] [Infrared absorption spectrum] (NaCl): vmax 2962, 2932,
2872, 1652, 1454, 1319, 983, 947, 740
Preparation of (Z,Z,E)-1-chloro-6,10,12-pentadecatriene (3)
[0047] Magnesium (13.7 g, 0.59 mol) and tetrahydrofuran (168 g)
were placed in a reaction vessel, and stirred at 60 to 65.degree.
C. for 30 minutes. After stirring,
(Z,Z,E)-1-chloro-3,7,9-dodecatriene (111.29 g, 0.56 mol) were added
dropwise thereto at 60 to 65.degree. C. and the reaction mixture
was stirred at 70 to 75.degree. C. for 2 hours to prepare
(Z3,Z7,E9)-3,7,9-dodecatrienylmagnesium chloride.
[0048] Copper (I) iodide (1.03 g, 0.0054 mol), triethyl phosphite
(2.34 ml, 0.014 mol), 1-bromo-3-chloropropane (92.29 g, 0.59 mol)
and tetrahydrofuran (56 g) were added to the reaction vessel and
the resulting mixture was stirred at 0 to 5.degree. C. for 30
minutes. After stirring, the tetrahydrofuran solution of
(Z,Z,E)-3,7,9-dodecatrienylmagnesium chloride prepared above was
added dropwise to the reaction mixture at 5 to 15.degree. C.
[0049] After completion of the dropwise addition, the resulting
mixture was stirred at 5 to 10.degree. C. for 40 minutes. Then,
ammonium chloride (6.40 g), an aqueous 20% by weight hydrogen
chloride solution (10.1 g) and water (175 g) were added to the
reaction mixture to terminate the reaction thereof. The water phase
was removed, while the organic phase was concentrated by removal of
tetrahydrofuran under reduced pressure. The residue was then
distilled under reduced pressure to obtain
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene (bp: 150 to 153.degree.
C./3 mmHg, 110.77 g, 0.46 mol) with a yield of 82.8%.
[0050] [Nuclear magnetic resonance spectrum].sup.1H-NMR (300 MHz,
CDCl.sub.3): .delta.1.02 (3H, t), 1.34-1.49 (4H, m), 1.78 (2H, tt),
2.02-2.16 (6H, m), 2.22 (2H, dt), 3.53 (2H, t), 5.27-5.34 (1H, m),
5.35-5.42 (2H, m), 5.72 (1H, dt), 5.97 (1H, dd), 6.30 (1H, dd);
[0051] .sup.13C-NMR (75.6 MHz, CDCl.sub.3): .delta.13.60, 25.87,
26.50, 27.04, 27.22, 27.65, 27.77, 32.52, 45.04, 124.57, 128.99,
129.21, 129.34, 129.94, 136.44
[0052] [Mass spectrum] EI-mass spectrum (70 eV): m/z 240(M.sup.+),
95, 79, 67, 55, 41, 29
[0053] [Infrared absorption spectrum] (NaCl): vmax 3006, 2933,
2857, 1652, 1460, 1311, 982, 946
Preparation of (Z,Z,E)-1,1-diethoxy-7,11,13-hexadecatriene (4)
[0054] Magnesium (5.65 g, 0.24 mol) and tetrahydrofuran (69 g) were
placed in a reaction vessel, and stirred at 60 to 65.degree. C. for
30 minutes. After stirring,
(Z,Z,E)-1-chloro-6,10,12-pentadecatriene (55.39 g, 0.23 mol) was
added dropwise thereto at 60 to 65.degree. C. and the resulting
mixture was stirred at 70 to 75.degree. C. for 2 hours to prepare
(Z,Z,E)-6,10,12-pentadecatrienylmagnesium chloride.
[0055] Toluene (119 g) and ethyl orthoformate (44.29 g, 0.30 mol)
were added to the reaction vessel at 75 to 85.degree. C. The
resulting mixture was stirred at 90 to 100.degree. C. for 8 hours.
Then, an aqueous 20% by weight hydrogen chloride solution (21.8 g)
and water (34.5 g) were added thereto to separate the reaction
mixture into phases. The organic phase was washed with an aqueous
sodium hydroxide solution, and concentrated by removal of the
solvent under reduced pressure to obtain
(Z,Z,E)-1,1-diethoxy-7,11,13-hexadecatriene (58.62 g, 0.19 mol)
with a yield of 81.8%.
[0056] [Nuclear magnetic resonance spectrum].sup.1H-NMR (300 MHz,
CDCl.sub.3): .delta.1.01 (3H, t), 1.20 (6H, t), 1.28-1.38 (4H, m),
1.57-1.63 (2H, m), 1.99-2.05 (2H, m), 2.08-2.15 (4H, m), 2.21 (4H,
dt), 3.48 (2H, q), 3.63 (2H, q), 4.47 (1H, t), 5.27-5.39 (3H, m),
5.70 (1H, dt), 5.96 (1H, t), 6.29 (1H, dd); .sup.13C-NMR (75.6 MHz,
CDCl.sub.3): .delta.13.59, 15.33, 24.63, 25.86, 27.17, 27.32,
27.81, 29.12, 29.60, 33.53, 60.78, 102.90, 124.60, 128.93, 128.98,
129.23, 130.38, 136.37
[0057] [Mass spectrum] EI-mass spectrum (70 eV): m/z
262(M.sup.+-46), 103, 95, 67, 47, 29
[0058] [Infrared absorption spectrum] (NaCl): vmax 2972, 2929,
2857, 1456, 1373, 1128, 1062, 982, 946, 735
Preparation of (Z,Z,E)-7,11,13-hexadecatrienal (5)
[0059] (Z,Z,E)-1,1-Diethoxy-7,11,13-hexadecatriene (49.36 g, 0.16
mol) and toluene (30 g) were placed in a reaction vessel and
stirred at 20 to 25.degree. C. for 30 minutes. After stirring, 10%
by weight hydrochloric acid (19.3 g) was added dropwise to the
reaction mixture at 20 to 25.degree. C., and stirred for one hour.
The reaction mixture was separated into phases. Then, the organic
phase was washed with an aqueous sodium bicarbonate solution, and
concentrated by removal of the solvent under reduced pressure to
obtain (Z,Z,E)-7,11,13-hexadecatrienal (30.47 g, 0.13 mol) with a
yield of 82.7%.
[0060] [Nuclear magnetic resonance spectrum].sup.1H-NMR (300 MHz,
CDCl.sub.3): .delta.1.01 (3H, t), 1.30-1.41 (4H, m), 1.63 (2H, tt),
2.00-2.07 (2H, m), 2.11 (4H, tt), 2.21 (2H, dt), 2.41 (2H, dt),
5.26-5.33 (3H, m), 5.70 (1H, dt), 5.96 (1H, dd), 6.29 (1H, dd),
9.75 (1H, t);
[0061] .sup.13C-NMR (75.6 MHz, CDCl.sub.3): .delta.13.57, 21.94,
25.84, 26.97, 27.31, 27.74, 28.73, 29.36, 43.82, 124.55, 128.96,
129.13, 129.24, 129.99, 136.40, 202.9
[0062] [Mass spectrum] EI-mass spectrum (70 eV): m/z 234 (M.sup.+),
95, 79, 67, 55, 41, 29
[0063] [Infrared absorption spectrum] (NaCl): vmax 2962, 2932,
2856, 1727, 1460, 1322, 983, 947, 739
[0064] Having thus described certain embodiments of the present
invention, it is to be understood that the invention defined by the
appended claims is not to be limited by particular details set
forth in the above description as many apparent variations thereof
are possible without departing from the spirit or scope thereof as
hereinafter claimed.
* * * * *