JP3231566B2 - Process for producing (1'E) -3,4-bis (1'-butenyl) tetrahydro-2-furanone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to cis- (1'E) -3,4 which is an inhabiting pheromone of citrus pests such as lemon and mandarin (insects of the family Biprorulus bibax Breddin) inhabiting Australia. Formula (A ') useful as a synthetic intermediate of -bis (1'-butenyl) tetrahydro-2-furanol

Embedded image The present invention relates to a novel method for producing cis- (1′E) -3,4-bis (1′-butenyl) tetrahydro-2-furanone represented by the formula:

More specifically, the following formula (C)

Embedded image 2 (Z) -hexene-1,4-diol of the following formula (D)

Embedded image From 2 (E) -hexene-1,4-diol of formula (B)

Embedded image [Wherein R represents a hydroxyl-protecting group] (3E, 7E) -5- (oxy-substituted methyl) -6-hydroxycarbonyl-3,7-decadiene, or the following formula (B ′)

Embedded image [Wherein R represents a hydroxyl-protecting group] cis- (3E, 7E) -5- (oxy-substituted methyl)-
6-hydroxycarbonyl-3,7-decadiene is formed and the compound of formula (E)

Embedded image Of the above formula (A ′) directly without passing through meso- (3E, 7E) -5,6-bis (hydroxymethyl) -3,7-decadiene. The present invention relates to a novel process for producing (1′-butenyl) tetrahydro-2-furanone.

[0003]

2. Description of the Related Art Conventionally, cis-
For the method for producing (1′E) -3,4-bis (1′-butenyl) tetrahydro-2-furanone, for example, meso- (3E, 7E) -5,6-bis which is a compound of formula (E) Several methods have been proposed for obtaining the compound of the formula (A ') by oxidizing this via (hydroxymethyl) -3,7-decadiene.

For example, method (a): 3 (E) -hexenoic acid is treated with a base (lithium diisopropylamide) and then with iodine to carry out an oxidative coupling reaction to form a succinic acid derivative, and further to convert the compound into a reducing agent (Lithium aluminum hydride) to give a compound of formula (E), which is then oxidized to synthesize a compound of formula (A ′) [Tetrahedron Letters, 33
(7), 891 to 894, 1992], (b) Method: Starting from a Diels-Alder reaction product of butadiene and maleic anhydride as a starting material, the compound of formula (E) is obtained through 11 steps, Synthesis of compound of formula (A ') by oxidation [Liebigs Ann. Chem. 1992, 1185
~ 1190], Method (c): (E) -3-hexenoic acid (E) -4 '-(t-butyldimethylsilyl) -1'- obtained from tetrahydropyranyl ether of propargyl alcohol
A method for synthesizing a compound of the formula (A ') by converting the compound of the formula (E) into a compound of the formula (E) via the compound of the formula (B') by utilizing the Claisen rearrangement reaction of ethyl-2'butenyl [liebigs Ann] Chem. 1993, 1287-1294]. The compound of formula (A) is also synthesized via the compound of formula (B) in the same manner as described above. In each of the methods (a) to (c), the compound of the formula (E) is oxidized to obtain the compound of the formula (A ′). In the oxidation reaction, expensive and highly toxic oxidizing agents such as silver carbonate / celite, manganese dioxide or pyridinium chlorochromate are used. In addition, the operation is complicated, and mass production is not always satisfactory.

[0005]

According to the above methods (a) to (c), cis- (1'E) -3 which is a compound of the formula (A ') is obtained by oxidizing the compound of the formula (E). , 4-Bis (1′-butenyl) tetrahydro-2-furanone. Since the above method uses the compound of formula (E) from which the trans form or the like is separated, the above-mentioned furanone compound which is the compound of formula (A ′) can be produced with high purity. However, the above method requires a long process from the compound of the formula (B ′) to the compound of the formula (A ′), and uses an expensive and highly toxic oxidizing agent to oxidize the lactone compound as the compound of the formula (A ′). In the method (c), there are disadvantages such as the need for anhydrous conditions in the reduction step, the use of a large amount of solvent in the oxidation step, and very complicated operations. It was not something to be done.

[0006]

Means for Solving the Problems Accordingly, the present inventors have:
Intensive research has been conducted in order to establish a new production method of an industrially advantageous compound of the formula (A ') which can solve the above-mentioned problems.
As a result, they have found that it is possible to provide a production method capable of synthesizing the furanone compound in one step by omitting the reduction and oxidation steps from the compound of the formula (B ′). According to this production method, an acid to be used may be a general acid and has an advantage that it can be produced at low cost. Particularly preferably, by selecting 2 (Z) -hexene-1,4-diol as a starting material, the amount of by-products of the trans isomer, which is an isomer of the compound of the formula (A ′), is extremely small, and the yield is high. It has been found that a compound of formula (A '), which is a cis form, can be synthesized with high purity.

The present invention provides the following formula (B ')

Embedded image [Wherein R represents a hydroxyl-protecting group] The cis- (3E, 7E) -5- (oxy-substituted methyl) -6-hydroxycarbonyl-3,7-decadiene represented by the formula is treated with an acid in an organic solvent. And the following formula (A ')

Embedded image A process for producing cis- (1′E) -3,4-bis (1′-butenyl) tetrahydro-2-furanone represented by the formula:

In the present invention, (cis-) (3E, 7E) -5- (oxy-substituted methyl) -6-hydroxycarbonyl-3,7-decadiene (compound of formula (B) or formula (B) B ') Compound) is disclosed, for example, in Japanese Patent Application No. 5-95409 and November 28, 1994.
Japanese Patent Application (Title of Invention: Meso- (3E, 7E)-)
Production method of 5,6-bis (hydroxymethyl) -3,7-decadiene).

In the present invention, the oxy substituent (R) in the oxy-substituted methyl group is not particularly limited as long as it has a hydroxyl group protecting function, and the following are exemplified.
t-butyldimethylsilyl group, dimethylethylsilyl group, isopropyldimethylsilyl group, t-butyldiphenylsilyl group, triisopropylsilyl group, triethylsilyl group, methoxymethyl group, tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, A tetrahydrofuranyl group, a 1-ethoxyethyl group or a benzyl group; Hereinafter, the case where the oxy substituent is a t-butyldimethylsilyl group will be described. Japanese Patent Application No. 5-95409 discloses that 2 (E) -hexene-1,4 is used as a starting material.
-Diol was used in a patent application filed on November 28, 1994 using (3E, 7E) -5- (t-butyldimethylsilyloxy) using 2 (Z) -hexene-1,4-diol as a starting material. A method for forming meso- (3E, 7E) -5,6-bis (hydroxymethyl) -3,7-decadiene via 6) -6-hydroxycarbonyl-3,7-decadiene is described in detail. The above method will be described next.

The compound of formula (C), 2 (Z) -hexene-1,4-diol, or the compound of formula (D), 2
(E) -Hexene-1,4-diol is reacted with, for example, t-butyldimethylsilyl chloride (hereinafter also referred to as TBSCl) in an organic solvent in the presence of a base to give a compound of the formula (F)

Embedded image [Wherein TBS represents t-butyldimethylsilyl] 1- (t-butyldimethylsilyloxy) -2
(Z) -Hexen-4-ol or compound of formula (G)

Embedded image [Wherein TBS represents t-butyldimethylsilyl] 1- (t-butyldimethylsilyloxy) -2
A first step of forming (E) -hexen-4-ol,
The compound of the formula (F) or the compound of the formula (G) is dissolved in an organic solvent,
Reacting with 3 (E) -hexenoic acid in the presence of dicyclohexylcarbodiimide (hereinafter also referred to as DCC) to obtain a compound of formula (H)

Embedded image [Wherein TBS represents t-butyldimethylsilyl] (3E, 2′Z) -3-hexenoic acid 4 ′-(t-
Butyldimethylsilyloxy) -1'-ethyl-2'-butenyl or a compound of formula (I)

Embedded image [Wherein TBS represents t-butyldimethylsilyl] (3E, 2′Z) -3-hexenoic acid 4 ′-(t-
(Butyldimethylsilyloxy) -1′-ethyl-2′-butenyl, a second step, after enolizing the compound of the formula (H) or the compound of the formula (I) in an organic solvent in the presence of a base, Trimethylsilyl chloride (hereinafter TMSC)
l)), followed by a transfer reaction, followed by hydrolysis to give the compound of formula (B) (3E, 7E) -5- (t-butyldimethylsilyloxymethyl) -6-hydroxy. Carbonyl-3,
The compound of formula (B) can be easily synthesized by the production method comprising the third step of forming 7-decadiene. The compound of the formula (B ′) can be easily obtained by purifying the compound of the formula (B). Hereinafter, the first to third steps for synthesizing the compound of the formula (B) or the compound of the formula (B ′) will be described in detail for each step.

Production method of the first step: [Formula (C) or compound (D)
Synthesis] The compound of the formula (C) or the compound of the formula (D), which is a raw material for synthesizing the compound of the formula (F) or the compound of the formula (G), is known, and can be synthesized by a conventionally proposed method. They can also be manufactured by the method that they have found.
Hereinafter, this manufacturing method will be described. Propagyl alcohol and ethyl vinyl ether or 2,3-
Reaction with dihydropyran produces ethoxyether or tetrahydropyranyl ether of propargyl alcohol. After reacting the product with ethylmagnesium bromide, it is reacted with propanal to give 1-ethoxyethoxy-2-hexyn-4-ol or 1-ethoxyethoxy-2-hexyn-4-ol.
-To produce tetrahydropyranoxy-2-hexyn-4-ol. The product is then treated with p-toluenesulfonic acid in methanol to produce 2-hexyne-1,4-diol. Furthermore, the compound of formula (C) can be obtained by subjecting the product to catalytic hydrogen reduction in the presence of a Lindlar catalyst to reduce the compound of formula (C) and a reducing agent such as lithium aluminum hydride. .

According to the first step, 2 (Z) -hexene-1,4-diol which is a compound of the formula (C) or a compound of the formula (D)
The compound 2 (E) -hexene-1,4-diol is reacted with t-butyldimethylsilyl chloride (TBSCl) in an organic solvent in the presence of a base, and the compound of formula (F) 1- (t- Butyldimethylsilyloxy) -2 (Z)
-Hexen-4-ol or a compound of formula (G) 1
-(T-Butyldimethylsilyloxy) -2 (E) -hexen-4-ol can be easily synthesized.

The reaction temperature and the reaction time of the reaction from the compound of formula (C) or (D) to the compound of formula (F) or (G) are, for example, about -30 ° C. to about 50 ° C., more preferably about 30 ° C. In the temperature range of 0 ° C. to about 30 ° C., about 1 hour to about 24 hours can be employed. The amount of TBSCl used can be in the range of about 1.0 mol to about 1.5 mol per 1 mol of the compound of formula (C) or (D).
Specific examples of the organic solvent used in this reaction include, for example, halogenated hydrocarbons such as dichloromethane, dichloroethane, and chloroform. The use amount of these organic solvents is preferably, for example, in the range of about 1 to about 100 parts by weight per 1 part by weight of the compound of the formula (C) or (D). As the type of base used in this reaction, for example, triethylamine, tributylamine,
Examples thereof include nitrogen-containing organic bases such as pyridine and imidazole. The amount used is, for example, in the range of about 1 mol to about 5 mol per 1 mol of the compound of the formula (C) or the formula (D). This reaction is carried out, for example, by using 4- (dimethylamino)
It is preferable to carry out the reaction in the presence of a reaction accelerator such as pyridine (hereinafter also referred to as DMAP). After completion of the reaction, distillation, washing,
The compound of formula (F) or (G) can be obtained in good yield and good purity by appropriately employing ordinary separation means such as extraction, drying and column chromatography.

Production method of the second step: [Formula (H) or compound (I)
Synthesis] According to the second step, the compound of formula (F) 1- (t
-Butyldimethylsilyloxy) -2 (Z) -hexene-
4-ol or 1- (t-butyldimethylsilyloxy) -2 (E) -hexen-4-ol, which is a compound of the formula (G), is dissolved in an organic solvent in the presence of dicyclohexylcarbodiimide (hereinafter also referred to as DCC). Reacting with (E) -hexenoic acid to obtain a compound of formula (H) (3E, 2′Z)
4 '-(t-butyldimethylsilyloxy) -1'-ethyl-2'-butenyl-3-hexenoic acid or (3E, 2'E) -3-hexenoic acid 4'- which is a compound of the formula (I)
(T-butyldimethylsilyloxy) -1′-ethyl-
2'-butenyl can be easily synthesized.

Although the reaction time varies depending on the reaction temperature,
For example, in a temperature range of about 0 ° C. to about 80 ° C., for about 1 hour to
About 10 hours can be adopted. The preferred amount of 3 (E) -hexenoic acid to be reacted is the formula (F) or the formula (G)
The range is about 1 mol to about 2 mol per 1 mol of the compound. Specific examples of the organic solvent used include, for example, halogenated hydrocarbons such as dichloromethane, dichloroethane, and chloroform. The amount of the organic solvent used is, for example, in the range of about 1 to about 100 parts by weight per 1 part by weight of the compound of the formula (F) or the formula (G). The amount of DCC used is preferably, for example, in the range of about 1 mol to about 5 mol per 1 mol of the compound of formula (F) or formula (G). This step is also preferably carried out in the presence of a reaction accelerator such as DMAP. After completion of the reaction, the compound of formula (H) or formula (I) is easily synthesized in good yield and high purity by appropriately employing ordinary separation means such as distillation, washing, extraction, drying, and column chromatography. .

Production method of the third step: [Synthesis of compound of formula (B)] According to the third step, the compound of the formula (H) (3E,
2'Z) -3-hexenoic acid 4 '-(t-butyldimethylsilyloxy) -1'-ethyl-2'-butenyl or (3E, 2'E) -3-hexenoic acid which is a compound of formula (I) After enolization of 4 '-(t-butyldimethylsilyloxy) -1'-ethyl-2'-butenyl with a base in an organic solvent, trimethylsilyl etherification with TMSCl, followed by a transfer reaction, followed by hydrolysis By doing so, (3E, 7E) -5- (t-butyldimethylsilyloxymethyl) -6-hydroxycarbonyl-3,7-decadiene which is a compound of the formula (B) is produced. The compound of the formula (B ′) is obtained by subjecting the compound of the formula (B) to column chromatography,
It is obtained by appropriately employing ordinary separation means such as distillation, and performing separation and purification.

The reaction temperature of the above enolization reaction is, for example, about -100 ° C to about 0 ° C, more preferably about -80 ° C.
A temperature range of about to -50C and a reaction time of about 0.5 to about 3.0 hours can be employed. Specific examples of the organic solvent used in this reaction include, for example, hexamethylene phosphoramide (HMPA), tetrahydrofuran (TH
F), dimethoxyethane, n-hexane, toluene, benzene, diethyl ether and the like. These solvents can be used alone or as a mixture. The amount of the organic solvent used is, for example, the compound of formula (H) or compound (I)
A preferred range is from about 1 to about 100 parts by weight based on parts by weight. As the type of base used in this reaction, for example, lithium hexamethyldisilazide (L
HMDS), lithium diisopropylamide, lithium tetramethylpiperazide, butyllithium, sodium hydride and the like. The amount used is, for example, about 1 mol to about 2 mol per 1 mol of the compound of the formula (H) or the formula (I). The produced enol compound can be subjected to the next enol etherification reaction and transfer reaction in the same reaction system without isolation.

In the enol etherification reaction and the transfer reaction in this step, the formed enol is subjected to trimethylsilyl etherification with TMSCl, and then the temperature is gradually raised to room temperature to effect the transfer. The reaction temperature and reaction time in the step of trimethylsilyl etherification with TMSCl can be, for example, about 0.1 hour to about 2 hours in a temperature range of about -100 ° C to about 0 ° C. Also, TMS
The amount of Cl used can be in the range of about 1 mol to about 3 mol per 1 mol of the compound of formula (H) or formula (I). Next, a transfer reaction is carried out by gradually raising the reaction system to room temperature, and after the transfer reaction, the reaction system is hydrolyzed with a dilute aqueous acid solution such as hydrochloric acid to obtain the cis- (3E, A compound containing 7E) -5- (t-butyldimethylsilyloxymethyl) -6-hydroxycarbonyl-3,7-decadiene in high purity is produced. In the present invention, either a compound of formula (B) or a compound of formula (B ') can be used as a starting material.
The compound of the formula (B ′) is obtained by purifying the compound of the formula (B) into only the cis form.

The present invention relates to a compound of the formula (B ′)
(3E, 7E) -5- (oxy-substituted methyl) -6-hydroxycarbonyl-3,7-decadiene in an organic solvent,
In this method, the compound is treated with an acid to remove the oxy substituent as a protecting group, and at the same time, lactonized to obtain a compound of the formula (A ′).

The reaction temperature of the process of the present invention varies depending on the reaction time, but is, for example, in the range of about 0 ° C. to 150 ° C., more preferably about 20 ° C. to 100 ° C., and the reaction time is about 0.5 ° C.
Hours to 16 hours, more preferably about 1 to 3 hours. Examples of the acid used include mineral acids such as hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and p-toluenesulfonic acid, and organic acids. The amount of the acid to be used is, for example, about 0.001 mol to 0.5 mol, more preferably about 0.005 mol to 0.05 mol, per 1 mol of the compound of the formula (B ′). Examples of the organic solvent include acetonitrile, benzene, toluene, tetrahydrofuran, methanol, ethanol and the like. The amount of the organic solvent used is about 2 parts by weight to 2 parts by weight per 1 part by weight of the compound of the formula (B ′).
A range of 0 parts by weight, more preferably about 3 parts by weight to 10 parts by weight is exemplified. For purification of the obtained compound of the formula (A ′), ordinary purification means such as silica gel column chromatography and distillation are employed.

Now, the present invention will be described in further detail with reference to Examples and Reference Examples. In each of the following examples,% means% by weight unless otherwise specified.

Reference Example 1 1- (t-butyldimethylsilyloxy) -2 (Z) -f
Synthesis of xen-4-ol [ compound of formula (F) compound] 58.0 g (0.500 mol) of compound (C), 60.7 g (0.600 mol) of triethylamine, DMA
To a solution of 3.05 g (25.0 mmol) of P in dry methylene chloride (850 ml) was added 82.9 g (0.550 m
ol) of TBSCl in dry methylene chloride (80 m
l) The solution is added dropwise within a temperature range of 10-20 ° C. After the dropwise addition, the mixture was further stirred at room temperature for 18 hours, poured into a saturated aqueous solution of sodium hydrogen carbonate, and methylene chloride (300 ml ×
Extracted in 2). The methylene chloride layer was washed with saturated saline, dried over magnesium sulfate, and concentrated. The obtained crude product (149 g) was distilled under reduced pressure to obtain 109 g of the desired compound of the formula (F). Boiling point: 78 ° C. to 79 ° C./2 mmHg Yield: 95%

[0022]

Reference Example 2 1- (t-butyldimethylsilyloxy) -2 (E) -f
Synthesis of xen-4-ol [compound of formula (G)] 75.0 g (0.647 mol) of compound (D), 78.5 g (0.776 mol) of triethylamine, DMA
In a mixture of 3.95 g (32.3 mmol) of P and 1.100 ml of methylene chloride, 107 g (0.
711 mol) in methylene chloride (100 ml) was added dropwise over 30 minutes while cooling with ice water. After further stirring at room temperature for 21 hours, the mixture is poured into a saturated aqueous solution of sodium hydrogen carbonate and the organic layer is separated. The aqueous layer is extracted with methylene chloride, combined with the organic layer, washed with saturated saline, dried over magnesium sulfate, and concentrated. The obtained crude product was distilled under reduced pressure to obtain 147 g of the desired compound of the formula (G). Boiling point: 86 ° C to 87 ° C / 2mmHg Yield: 99%

[0023]

Reference Example 3 4 '-(t-butyl) (3E, 2'Z) -3-hexenoic acid
Dimethylsilyloxy) -1'-ethyl-2-butenyl
Compound of formula (F) 103.5 g (0.450 mol ) of compound of formula (H)
CC 111.4 g (0.540 mol), DMAP5.
A solution of methylene chloride (100 ml) containing 66.8 g (0.585 mol) of 3 (E) -hexenoic acid was added to a solution of 50 g (45.0 mmol) in dry methylene chloride (2000 ml) under ice water cooling at 7 ° C to 16 ° C. And dripping. After the dropwise addition, the mixture was further stirred at room temperature for 5 hours.
It was poured into hydrochloric acid (1000 ml) and methylene chloride (50 ml) was added.
0 ml x 1). The methylene chloride layer was washed with water, a saturated aqueous solution of sodium hydrogencarbonate and saturated saline, then dried over magnesium sulfate and concentrated. The obtained residue (270 g) was diluted with a mixed solvent of n-pentane (1000 ml) and diethyl ether (400 ml), and allowed to stand in a refrigerator (0 to 5 ° C.) for 12 hours. Separately, the filtrate was concentrated under reduced pressure. The obtained crude product (186 g) was subjected to silica gel column chromatography and distillation under reduced pressure several times. 114.1
g of the desired compound of formula (H) was obtained. Boiling point: 110 ° C to 112 ° C / 1 mmHg Yield: 78%

[0024]

Reference Example 4 4 '-(t-butyl) (3E, 2'E) -3-hexenoic acid
Dimethylsilyloxy) -1'-ethyl-2-butenyl
Compound of formula (G) 69.0 g (0.300 mol) of [formula (I) compound] , DC
C 74.3 g (0.360 mol), DMAP 3.67
g (30.0 mmol) and 1400 ml of methylene chloride
3 (E) -hexenoic acid 44.5 into a mixture of
g (0.390 mol) of methylene chloride (140 ml)
The solution is added dropwise in one hour. After further stirring at room temperature for 3 hours, the mixture is poured into dilute hydrochloric acid and extracted with methylene chloride. The organic layer is washed with water, a saturated aqueous solution of sodium hydrogen carbonate and water again, dried over magnesium sulfate and concentrated. The residue is diluted with a mixed solvent of n-pentane and ether, insolubles are removed by filtration, and the filtrate is concentrated. The obtained crude product was distilled under reduced pressure,
85 g of the desired compound of formula (I) was obtained. Boiling point: 132 ° C. to 133 ° C./2 mmHg Yield: 87%

[0025]

Reference Example 5 (3E, 7E) -5- (t-butyldimethylsilyloxy)
Methyl) -6-hydroxycarbonyl-3,7-decadi
Synthesis of ene [compound of formula (B)] Under argon atmosphere, 100 ml (100 mmol) of a 1.0 M LHMDS THF solution and 420 ml of dry THF
27.1 g (83.3 mm) of the compound of formula (H)
ol) in dry THF (10 ml).
It was added dropwise at ° C. After stirring at the same temperature for 3 hours, 12.7 g
Dry THF containing TMSCl (0.117 mol) and triethylamine 1.18 mg (11.7 mmol)
(2 ml) The suspension was added dropwise at -68 ° C to -65 ° C. After stirring at the same temperature for 15 minutes, the temperature was raised to room temperature over time. The mixture was further stirred at room temperature for 1 hour. The reaction mixture was poured into 1N hydrochloric acid saturated with sodium chloride (200 ml), and THF was added.
The layers were separated and the aqueous layer was extracted with ethyl acetate (300ml × 2). The organic layer was combined with the extract, washed with saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure to obtain the compound of formula (B). Yield: 100% IR (thin film) ν _max (cm ⁻¹ ): 3600 to 240
0 (br, m), 1705 (s), 1460 (m,
), 1250 (s), 1210 (m), 1110
(S), 970 (m), 835 (s), and 775 (s).

[0026]

Reference Example 6 (3E, 7E) -5- (t-butyldimethylsilyloxy)
B) -6-hydroxycarbonyl-3,7-decadiene
[Synthesis of compound of formula (B)] THF of 1.0 M-LHMDS 3.3 ml (3.3 mm
ol) with 4.8 ml of HMPA and 12.7 ml of THF
In a mixed solution of 0.98 g (3.0 mmol) of the compound of the formula (I).
l) in THF (0.5 ml) at -70 ° C to -68.
C., dropwise over 5 minutes. After stirring at the same temperature for 100 minutes, 0.42 g of trimethylsilyl chloride (3.9 mm
ol) and triethylamine 40 mg (0.39 mmol)
1) A suspension of THF (1 ml) was added, cooling was stopped, and the temperature was raised to room temperature. After stirring at room temperature for 10 hours, the reaction mixture was poured into dilute hydrochloric acid saturated with sodium chloride and extracted with ether.
The organic layer was washed with saturated saline, dried over magnesium sulfate, and concentrated to obtain 0.93 g of the compound of the formula (B). Yield: 95%

[0027]

Reference Example 7 (3E, 7E) -5 obtained in Reference Example 5
(T-butyldimethylsilyloxy) -6-hydroxycarbonyl-3,7-decadiene (compound of formula (B))
(4.9 g, 15 mmol) in acetonitrile (25 m
l) To the solution, 46% hydrofluoric acid (1.3 ml) was added, and the mixture was heated under reflux for 2 hours. After cooling, the reaction mixture was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 2.7 g.
Was obtained (yield 93%). Cis isomer: trans isomer: 95: 5 Refractive index: n ²⁴ _D : 1.4752

Embedded image

[0028]

Reference Example 8 (3E, 7E) -5 obtained in Reference Example 6
(T-butyldimethylsilyloxy) -6-hydroxycarbonyl-3,7-decadiene (compound of formula (B))
(5.9 g, 20 mmol) of methanol (30 ml)
To the solution was added p-toluenesulfonic acid (0.12 g), and the mixture was stirred at room temperature for 3 hours. The methanol was once distilled off under reduced pressure, 30 ml of benzene was added to the obtained residue, and the mixture was heated under reflux for 2 hours. After cooling, the reaction mixture was poured into a saturated aqueous solution of sodium hydrogen carbonate, extracted with ethyl acetate, and the ethyl acetate layer was washed with saturated saline. After drying over magnesium sulfate, the mixture was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 3.5 g of the compound of the formula (A) (yield: 91%). Cis-form: trans-form = 87: 13

[0029]

Example 1 (3E, 7E) -5 obtained in Reference Example 5
(T-butyldimethylsilyloxy) -6-hydroxycarbonyl-3,7-decadiene (compound of formula (B))
(2.1 g, 6.4 mmol) was separated and purified by medium pressure silica gel column chromatography (silica gel: 100 g), and cis- (3E, 7E) -5- (t-butyldimethylsilyloxy) -6-hydroxycarbonyl- 3,7-
1.7 g of decadiene (compound of formula (B ')) (yield 81
%)Obtained. This was treated in the same manner as in Reference Example 7 to give cis- (1′E) -3,4-bis (1′-butenyl) tetrahydro-2-furanone (compound of formula (A ′))
0.91 g (yield 90%) was obtained.

[0030]

Example 2 The compound of the formula (B) obtained in Reference Example 6 (3.
(3 g, 10 mmol) was separated and purified by medium pressure silica gel column chromatography (silica gel: 165 g) to obtain 2.3 g (yield: 70%) of the compound of the formula (B '). This was treated in the same manner as in Reference Example 8 to obtain 1.3 g (yield 92%) of the compound of the formula (A ′).

[0031]

According to the present invention, (cis-) (3E, 7
E) From (5- (oxy-substituted methyl) -6-hydroxycarbonyl-3,7-decadiene [compound of formula (B ')], (cis-) (1'E) -3 is obtained in only one step in good yield. ,
4-bis (1′-butenyl) tetrahydro-2-furanone [compound of formula (A ′)] can be produced. The compound of the formula (A ′) inhabits Australia and is a citrus pest such as lemon or mandarin (Hemiptera: Biprorulus bibax
Cis- (1'E)-, an attractive pheromone of Breddin)
It is useful as an intermediate for the synthesis of 3,4-bis (1'-butenyl) tetrahydro-2-furanol.

──────────────────────────────────────────────────続 き Continued on the front page (56) References Liebigs Ann. Chem. , (1993), (12), p1287-1294. T. MORRISON, R.A. N. Boyd, Translated by Koji Nakanishi et al., "Morrison Boyd Organic Chemistry (Middle) 5th Edition", Tokyo Kagaku Dojin, issued October 2, 1989, 5th edition, 2nd print, pp. 1057-1059, 1094- 1096 (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 307/33 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. The following formula (B ′): [Wherein R represents a hydroxyl-protecting group] cis- (3E, 7E) -5- (oxy-substituted methyl) -6-hydroxycarbonyl-3,7-decadiene represented by the following formula: The following formula (A ′): A method for producing cis- (1′E) -3,4-bis (1′-butenyl) tetrahydro-2-furanone represented by the formula: