JPS62215580A - Novel tetrahydropyranyl ether - Google Patents

Abstract

NEW MATERIAL:1-(Tetrahydropyran-2-yloxy)-11-dodecene of formula I. USE:A synthetic intermediate of 11-dodecenyl acetate, a major component of the sex pheromone of tea leaf folder (Homona magnanima DIAKONOFF). The use of the compound enables the large-amount production of the pheromone. PREPARATION:Only one hydroxyl in 1,12-dodecanediol of formula II is halogenated according to a usual manner to give 12-halododecanol of formula III (X is halogen). The remaining hydroxyl is protected with a tetrahydropyranyl group to form 12-halo-1-(tetrahydropyran-2-yloxy)dodecane. The product is allowed to react with a base such as potassium t-butoxide in an organic solvent such as dimethyl sulfoxide at room temperature, when needed, at 0 deg.C to the boiling point of the solvent to give the compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel tetrahydropyranyl ether 4, and more specifically, the present invention relates to a novel tetrahydropyranyl ether 4. The present invention relates to a novel 1-(tetrahydropyran-2-yloxy)-11-dodecene that is useful as an intermediate for its production, and a method for producing the same.

(Prior art) In recent years, the use of sex pheromones has been widely researched as a pest control method, and has been widely used in agricultural products such as tea,
Communication disruption methods and mass trapping methods have been widely researched as methods for controlling the pest insect pest of various garden plants.

Chabamaki sex pheromones include cis-11-tetradecenyl acetate, cis-9-dodecenyl acetate, 11
-dodecenyl acetate, etc., of which 1
1-dodecenyl acetate can be prepared by a method already known for cis-9-tetradecenyl acetate (D
, Warthen, J., Med.

Che, 11.371 (1968)), the terminal hydroxyl group was protected according to the following formula (where X is a halogen atom and R is a hydroxyl group-protecting group). 1-Decanol, for example, tetrahydropyranyl ether protected with a tetrahydropyranyl group, is reacted with lithium acetylide in liquid ammonia to obtain an acetylene derivative, which is deprotected, catalytically hydrogenated, and then acetylated. It is manufactured by.

However, according to the above method, it is necessary to carry out the reaction at a low temperature of about -30°C using liquid ammonia, and when producing in large quantities, a production equipment with pressure resistance is required. Furthermore, since the above reaction needs to be carried out in the absence of water, operations such as dehydration of the raw materials used and drying of the reaction apparatus are extremely cumbersome.

(Object of the Invention) As a result of intensive research to solve the above-mentioned problems in the production of 11-dodecenyl acetate, the present inventors found that
The present invention was achieved by discovering a novel tetrahydropyranyl ether as a suitable intermediate raw material for easily producing 11-dodecenyl acetate in large quantities.

(Structure of the invention) The novel tetrahydropyranyl ether according to the present invention is
1-(tetrahydropyran-2-yloxy)-11-
It is dodecene and is represented by the following structural formula.

The above tetrahydropyranyl ether according to the invention can be prepared according to the invention according to the following scheme.

(X indicates a halogen atom.) According to the method of the present invention, first, only one hydroxyl group of 1,12-dodecanediol (2) is substituted with halogen, and 1
2-halodecanol (3) is prepared, the remaining hydroxyl group is protected with a tetrahydropyranyl group to obtain 12-halo-1-(tetrahydropyran-2-yloxy)dodecane (4), and then a base is added to this. By dehydrohalogenation, 1-(tetrahydropyran-2-yloxy)-11-dodecene (11) according to the invention can be obtained.

Each of the above steps will be explained in detail below.

1.12-Dodecanediol (2) is easily available as a commercial product. By halogenating only one hydroxyl group according to a conventional method, 12-halodecanol (3) is obtained. Here, examples of the halogen include chlorine, bromine, and iodine, but chlorine or bromine is particularly preferred from the viewpoint of yield of the target product by dehydrohalogenation reaction and cost.

For example, 12-chloro-1-dodecanol is 1°12
It can be obtained by dissolving -dodecanediol (2) in a hydrocarbon solvent such as hexane, heptane, benzene, toluene, etc., mixing this with concentrated hydrochloric acid, and reacting at reflux temperature. In this case, it is necessary to use hydrochloric acid in an amount of 1 equivalent or more based on 1,12-dodecanediol,
Preferably a large excess of 5 to 100 equivalents is used. After the reaction, the desired 12-chloro-1-dodecanol (3) can be obtained from the organic layer.

Alternatively, a chlorinating agent such as thionyl chloride or phosphorus trichloride may be added to an organic solution of 1,12-dodecanediol.
．． If 2 to 2 equivalents, preferably 0.8 to 1.2 equivalents are added and reacted, 12-chloro-1-dodecanol (3) can be obtained.

12-bromo-1-dodecanol can also be obtained by a similar method. In the case of the former method mentioned above,
A concentrated hydrobromic acid aqueous solution may be used instead of concentrated hydrochloric acid, and in the case of the latter method, for example, phosphorus tribromide may be used as the brominating agent.

Next, the remaining hydroxyl group of 12-halo-1-dodecanol (3) was protected with a tetrahydropyranyl group to obtain 12-halo-1-dodecanol (3).
-halo 1-(tetrahydropyran-2-yloxy)
Dodecane (4) is obtained. A method of using such a tetrahydropyranyl group as a protecting group is, for example, Protect
ive Groups in Organic 5yn
thesis.

T, W, Greene, Jotu++ Wile
y & 5ons+ New York (1981), it is already well known, and the present invention can also be carried out by an appropriate method. for example,
Dissolve 12-halo 1-dodecanol in a solvent such as methylene chloride or tetrahydrofuran, and add 1 to 2 times the amount of 2
．． 3-dihydropyran may be reacted in the presence of a catalytic amount of p-)luenesulfonic acid.

Dehydrohalogenation of 12-halo 1-(tetrahydropyran-2-yloxy)dodecane (4) to obtain the novel 1-(tetrahydropyran-2-yloxy)-11-dodecene+1) according to the invention: The above compound (4) is reacted with a base in an appropriate organic solvent.

Any organic solvent can be used as long as it does not have a harmful effect on the reaction, but preferably,
Hydrocarbon solvents such as hexane, benzene, and toluene, alcohols such as methanol, ethanol, and butanol, ethers such as diethyl, ether, and tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, and the like are used.

Examples of bases that can be used include alkali metal alkoxides such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, potassium t-butoxide, alkyl lithiums such as butyl lithium, hydrogenated Examples include metal hydrides such as sodium, organic amines such as triethylamine, N,N-dimethylaminopyridine, and quinuclidine. Among these, potassium t-butoxide can be particularly preferably used in terms of ease of handling and yield of the target product (1).

The amount of these bases used is not particularly limited, but usually 0.5 to 1
0 equivalent, preferably 1 to 5 equivalents. The base is usually
Suitable organic solvents that do not have a detrimental effect on the reaction, e.g.
Dissolve in dimethyl sulfoxide, methanol, ethanol, butanol, etc. to make a solution, and add 12-halo
It is advantageous in terms of reaction operation to add it to an organic solution of dodecanol.

The reaction temperature may normally be room temperature, but if necessary, it may be 0°C.
The temperature may range from the boiling point of the solvent used.

After the completion of the reaction, water is added to the reaction mixture, the organic layer is separated, and the tetrahydropyranyl ether (1) according to the present invention can be obtained by a conventional purification method such as chromatography or distillation.

The tetrahydropyranyl ether (1) thus obtained can be reacted with water or alcohol in the presence of an acid catalyst to eliminate the tetrahydropyranyl group according to the following formula (Ac represents an acetyl group). te, 1
By preparing 1-dodecen-1-ol (5) and then acetylating this in a conventional manner, 11-dodecenyl acetate (6) can be obtained. For example, 11-dodecenyl acetate (6) can be obtained by reacting 11-dodecen-1-ol (5) with acetic anhydride using pyridine as a solvent.

(Effects of the Invention) As described above, by using 1-(tetrahydropyran-2-yloxy)-11-dodecene according to the present invention as an intermediate raw material, 11-dodecene, which is a main component of the Chabamaki sex pheromone, can be used as an intermediate material. Nyl acetate can be easily produced in large quantities.

(Example) The present invention will be explained below with reference to Examples.

50 g of 12-chloro-1-dodecanol (3)
(247 mn+ol) of 1,12-dodecanediol (2) 200 mm of concentrated hydrochloric acid and 200 ml of heptane were mixed and stirred at reflux temperature during the day and at room temperature during the night for 8 days. The heptane layer was separated, washed with saturated brine, dried over magnesium sulfate, filtered, and concentrated to obtain 12-chloro-1 as a crude product.
-dodecanol (3143.0 g (yield 78.9%)) was obtained.

2. Spectrum (ν+eax) 3320 (m
), 2910(s), 2840(s), 1460
(m), 1370(w).

1300 (w), IQ5Q (m), 720 (m),
650 (m).

This was used in the next reaction without purification.

12-chloro-1-dodecanol (3) 43.0 g
was dissolved in 400 ml of methylene chloride, and 19.7 g (234+++ mol) of dihydrobilane and 111
-) 300 μl of luenesulfonic acid was added and stirred at room temperature for 3 days. This was followed by washing with saturated aqueous sodium bicarbonate solution, drying over sodium sulfate, filtering, and concentrating.
67.1 g of 12-chloro-1-(tetrahydrobilan-2-yloxy)dodecane (4) was obtained as a crude product.

This was subjected to column chromatography (Wakogel (nee 2)
00 (600g), hexane/ether (9/1))
Purified by treatment, purified 12-chloro-1-(tetrahydropyran-2-yloxy)dodecane (4) 37゜1
g (yield: 62.4%).

2. Evening spectrum (νll1mX) 2920(s
), 2850(s), 1460(m), 1440
(m), 1350 (m).

1320(w), 1280(w), 1260(w)
, 1200(m), 1180(w).

1160(w), 1135(m), 1120(Il
l), 101075(, 1030(n+).

980(m), 900(w), 865(w), 8
10 (%*), 720 (w), 650 (ka)
.

At the same time, 5.0 g of 1,12-dichlorododecane was separated as a by-product.

12-chloro-1-(tetrahydropyran-2-yloxy)dodecane (4) 20 g (65.7 mmol
) was dissolved in 130 ml of benzene. 14.6 g of potassium t-butoxide was dissolved in 130 m of dimethyl sulfoxide.
A solution of IN potassium t-butoxide dissolved in 1 was added dropwise to the above solution at room temperature. After stirring at room temperature for 10 minutes, the mixture was poured into water and extracted with ether.

After washing this ether layer with water, it was dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 19.5 g of 1-(tetrahydropyran-2-yloxy)-11-dodecene (1) as a crude product. Ta. This was purified by column chromatography (Wako Gel C-200 (400 g), hexane/ether (9/1)), and purified 1-(
16.4 g (yield 93.1%) of tetrahydropyran-2-yloxy)-11-dodecene (1) was obtained.

Figure 1 shows 1-(tetrahydropyran-2-yloxy)
The infrared absorption spectrum of -11-dodecene and the second
The figure shows the proton nuclear magnetic resonance spectrum.

1 standing 130-135℃ 10.15 fight ng Hogo! no”
1.4562, Ta spectrum (νLLL) 3080(w), 2930(s), 2860(s)
, 1640(a+), 1465(n+).

1450 (m), 1440 (m), 1355 (m)
, 1325(m), 1285(m).

1260(m), 1205(n+), 1135(s
), 1125(s), 1080(s).

1030(s), 990(m), 910(s),
870(Ill), 815(Ill), 720(w
), 630 (w).

Proton f-goods vector (δ(CDCh))1
．． 0-1.9 (22H, m), 1.95-2.10
(211, m), 3.30-3.55 (211,
m), 3.65-3.80 (111, m), 3.
85-3.95 (Iff, n+), 4.57 (1
11, br, s), 4.90-5.05 (28°n+), 5.75-5.90 (IH, +n).

Bean i minute history C+, actual measured value as HsgOz C: 76.15. H: 12.13 calculated value
C: 76.06. H: 12.02 An example of the synthesis of 11-dodecenyl acetate using tetrahydropyranyl ether according to the present invention is shown below as a reference example.

Reference example 11-dodecen-1-ol 1-(tetrahydropyran-2-yloxy)-11-
Dodecene (1) 15.0 g (56.0m+mol
) was dissolved in 150 ml of methanol, and 100 ml of p-toluenesulfonic acid was added. After stirring overnight at room temperature, saturated aqueous sodium hydrogen carbonate solution was added to stop the reaction, and the mixture was concentrated. Water was added to the residual liquid, extracted with ether, and the ether layer was washed with saturated brine, dried over magnesium sulfate, filtered, and concentrated to obtain 11-dodecene-1 as a crude product. -Oil 9.71 g was obtained. Column chromatography (Wako gel C-200 (10
0 g) and hexane/ether (8/1) treatment to obtain 9.65 g (yield 93.5%) of purified 11-dodecen-1-ol.

2. Line absorption spectrum (ν1.X) 3330 (m), 3080 (w), 2930 (s)
, 2860(s), 1640(w).

1460 (m), 1055 (+m), 990 (m)
, 910(m), 710(w).

630 (w).

Mix 8 g (43,5++nol) of 11-dodecen-1-ol of 11-dodecenyl acetate (6), 10 ml of pyridine, and 10 ml of acetic anhydride, stir at room temperature for 3 days, and then add water to the mixture. The reaction was stopped by stirring at room temperature for 30 minutes. After extraction with ether, the ether layer was washed with IN hydrochloric acid and saturated aqueous sodium bicarbonate solution, and then dried with magnesium sulfate. filter, concentrate,
Column chromatography (Wako gel c-200 (1
00g) and hexane/ether (9515)) treatment to obtain 113.90g of 11-dodecenyl acetate. This was further purified by vacuum distillation to obtain 8.34 g of purified 11-dodecenyl acetate (6) (yield 84.8%).
) was obtained.

1 point 98.5~b, spectrum (νlI□) 3080(w), 2930(s), 2850(s)
, 2740(s), 1640(m).

1460 (m), 1390 (+w), 1365 (m
), 1240(s), 101035(.

995 (m), 910 (+m), 720 (w),
630(w), 605(w).

Proton − vector (δ(CDC13))1.
2-1.4 (L4H,ta, (CHz)t), 1
．． 55-1.65 (2H, m.

-CHzCOAc), 2.03 (3H,s, C0C
H5) 11.99-2.07 (2H, r@, □C-C
Hg-), 4.03 (2H,t, J=6.811
z.

-CHzCOAc) + 4.93 (IIl, d,
J-10H2, terminal olefin H (trans), 4.
97 (IH, dd, J-1711z.

J=1.5Hz, terminal olefin H (cis), 5.7
9 (18, ddd, J-17H2, J=10H2, J
-6,3H2, -C-CB-).

'3C f-Lis vector (δ(CDCI)) 21.0
．． 26.0. 28.7. 29.0. 29.2.
29.3. 29.5'.

29.5', 33.8. 64.7. 114.1
．． 139.2. 171.2° Gas chromatography (column: phenylmethyl silicone (25ms +
0.2m), 150℃, carrier gas: helium (0.7s+l/1lin,) Rt 13.33w
in, (99,5χ) Comparative Example 12-p-toluenesulfonyl-1-(tetrahydropyran-2-yloxy)dodecane Ig (2°27a+s
+ol) was dissolved in 6 ml of benzene, and 13 s of a dimethyl sulfoxide solution of IN potassium t-butoxide was added to this.
+1 was added dropwise to the above solution at room temperature. After stirring at room temperature for 10 minutes, the mixture was poured into water and extracted with ether.

After washing this ether layer with water, it was dried over anhydrous magnesium sulfate, and the reaction product was analyzed by gas chromatography. The yield of the desired tetrahydropyranyl ether (1) was only 7%, and the remaining is 12-t-
It was butoxy-1-(tetrahydropyran-2-yloxy)dodecane (7). Concentrate the above ether layer,
Column chromatography gave 717 ml of the above compound (7) (yield 93%).

[Brief explanation of drawings]

FIG. 1 shows 1-(tetrahydropyran-2) according to the present invention.
Figure 2 shows the infrared absorption spectrum of -yloxy)-11-dodecene and its proton nuclear magnetic resonance spectrum.

Claims (1)

[Claims] (1) 1-(tetrahydropyran-2-yloxy)-11-dodecene represented by the structural formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼.