JPS6160630A - Preparation of aldehyde derivative - Google Patents

Abstract

PURPOSE:To prepare (11E, 13E)-11,13-hexadecadienal useful as a sex pheromone of grass moth (Oebia undails Fabricius), economically in an industrial scale, in high yield, by heating a specific novel compound in the presence of an alkali, and oxidizing the product. CONSTITUTION:The objective compound of formula V can be prepared by (1) reacting 3-sulfolene of formula I with 10-tetrahydropyranyloxydecyl halide and an ethyl halide in the presence of a base, (2) treating the resultant compound of formula II (THP is tetrahydropyranyl) with an acid, (3) heating the obtained novel 10-(5-ethyl-3-sulfolen-2-yl)decan-1-ol in the presence of an alkali to obtain the (E,E)-diene alcohol of formula IV in high stereoselective yield, and (4) oxidizing the OH group of the compound with an oxidizing agent. EFFECT:The objective compound can be prepared in short steps from easily available 3-sulfolene via a novel compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aldehyde derivatives, and more specifically, the present invention relates to a method for producing aldehyde derivatives, and more specifically, the present invention relates to a method for producing aldehyde derivatives, and more specifically, the present invention relates to a method for producing an aldehyde derivative, and more specifically, the present invention relates to a method for producing an aldehyde derivative, and more specifically, a method for producing an aldehyde derivative having the following formula (
I) (11E, 13E).

The present invention relates to a method for producing 13E)-11,13E)-11,13-hexadecadienal (hereinafter referred to as an aldehyde compound).

Since the larvae of the Japanese spotted moth cause serious feeding damage to cruciferous vegetables such as radish and cabbage, effective control is desired.

The above aldehyde compounds, which are the subject of the present invention, are known as sex pheromones (Agr, Biol, Che
m,, 46, 2395-2397 (1982))
.

By using the sex pheromone in a moth-attracting device that uses it as an attractant, it becomes possible to predict the density of occurrence of the spotted moth.

By the way, it becomes possible to predict the density of occurrence of pests.

By the way, if we could predict the density of pests,
Predicting the density of pests is an extremely important technique, especially in modern comprehensive pest control systems, because it makes it possible to spray effective insecticides at the appropriate time and thereby efficiently eradicate target pests. be.

The present inventors have conducted intensive studies on a method for industrially advantageous production of the sex pheromone of the Japanese spotted moth, and have found that 10-(5-ethyl-8-sulfolene-2-
(11E, 1i11E)-11,13-hexadecadiene of the formula (It) C2H4k'1 stereoselectively and in high yield by heating decane-1-ol in the presence of an alkali. The inventors have discovered that -1-ol is obtained and then the desired aldehyde compound can be obtained easily and in good yield by oxidizing the hydroxyl group of the compound, leading to the present invention.

In the method of the present invention described above, the formula (11E, 1
The alcohol compound represented by 3+) is a new compound, and is obtained by introducing a 10-tetrahydrobyranyloxydecide group and an ethyl group into 8-sulfolene represented by formula (VI) in the presence of a base. (IV) [Wherein, P represents a tetrahydropyranyl group] It can be obtained by treating 2-(10-tetrahydropyranyloxydecyl)-5-ethyl-8-sulfolene with an acid.

Up to now, as a method for producing the aldehyde compound represented by the above formula (I), Hydrosia L/
:) 2JL/ification (hydrozirconation)
) reaction and acetylene dituber reaction (acety
However, this method is disadvantageous in that it uses an acetylene-based synthetic intermediate that is difficult to handle industrially, and that it uses an expensive noble metal catalyst or a noble metal reagent. It is not necessarily advantageous, and the yield is not satisfactory.

On the other hand, according to the method of the present invention, the desired aldehyde compound can be produced in an extremely short process and in good yield using easily available 8-sulfolene as a starting material, which is extremely advantageous from an industrial standpoint. In particular, the method of the present invention can be said to be extremely advantageous in that an isomer component having attracting activity, ie, an (E,E)-diene, can be obtained with high stereoselectivity.

The method of the present invention will be explained below. When obtaining the tetrahydropyranyl ether compound represented by formula (N) from 3-sulfolene represented by formula (VT), 10-tetrahydropyranyloxydecyl is used as a reagent for introducing lO-tetrahydropyranyloxydecyl group and ethyl group, respectively. Examples include lO-tetrahydropyranyloxydecyl halide such as iodide and ethyl halide such as ethyl iodide, and any of these may be reacted first. Examples of the base present during the reaction include organic bases such as lithium hexamethyldisilazane (L i HMDS ) and lithium diisopropylamide. The reaction is carried out in the presence of a cation scavenger. Further, the reaction is usually carried out in an organic solvent such as tetrahydrofuran (Tt(F)) under cooling.

The tetrahydropyranyl ether compound obtained at 1% in this manner is easily removed by the action of a mineral acid such as hydrochloric acid or an organic acid such as p-toluenesulfonic acid in a conventional manner, and the tetrahydropyranyl group can be easily removed to form the formula (m). This leads to the alcohol compound shown in

Next, the alcohol is thermally cleaved while smoothly releasing sulfur dioxide gas by heating the compound in a protic solvent such as ethanol or methanol in the presence of an alkali such as potassium hydroxide or potassium carbonate. The desired (E,E)-diene alcohol represented by formula (n) is stereoselectively obtained almost quantitatively.

The 1EN(E,E)-diene alcohol is then treated with, for example, pyridinium chromylchromate (FCC).
The desired aldehyde compound can be easily obtained by reacting with a common oxidizing agent used to convert a hydroxyl group into a formyl group.

EXAMPLES The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example ■ 10-(5-ethyl-8-sulfolen-2-yl)
Synthesis of decan-1-ol 3-sulfolene 26.6F, 10-tetrahydropyranyloxydecyl iodide 41.4f and HMPA7
0- was dissolved in dry THF 600- and cooled to -78°C.Then, Li-S20.Tf was dissolved in dry THF (
After dissolving in F3Q- and cooling to -78°C, this was added all at once to the previously prepared TI(F solution) under reduced pressure and stirring, and stirred at -78''C for 1 hour.

Next, while gradually raising the temperature of the reaction solution, 100 s of saturated saline solution was added at -20°C, and then the temperature of the solution was raised to room temperature. After concentrating the reaction solution under reduced pressure and distilling off most of the THF, 100% of water was added and extracted with methylene chloride. The methylene chloride skin was dried over anhydrous sodium sulfate and concentrated, and the residue was subjected to column chromatography packed with 250 f of silica gel (Wako C-200) (eluent: ethyl acetate:n-hexane-1:9). -(10-tetrahydropyranyloxydecyl)-8-sulfolene22.
69F (yield: 55%) was obtained.

1HNMR (CDCza) δ(+)1)m) 1.20 to 2.20 (24H, m)
111.65 (2H, S, 5-H) 8.20-4
．． 00 (5H, m) 4.60 (LH, m) 6.05 (2H, s, 8-H, 4-H) IR (CHCt
a) 13E) 10, 1140 1MS m/
857(M”-1) 2-(10
-tetrahydropyranyloxydecyl)-8-sulfolene 7.35f1 ethyl iodide 1.88- and HMPA7
．． 2- was dissolved in 100 ml of dry THF, and then added to the dry Tf of LiHMDS 3.81 in the same manner as above.
(After adding the F solution, the same treatment was performed to obtain 5.06N of 2-(10-tetrahydropyraniloxydecyl)-5-ethyl-8-sulfolene (yield: 67%).

'HNMR(CDCts) δ(pm)m) 1.01(BF(,t,J-7,0
H2) 1.15-2.20 (26H, m) 8.20-4.05 (6H, m) 4.62 (IH,, m).

5.98 (2H,S, 8.4-H)IR(CHC
tg)iaoo, 1100 cm 'MS''/
887 (M +1) then 2-(10
-tetrahydropyranyloxydecyl)-5-ethyl-8
After normal post-treatment, the desired 10-(
5-ethyl-8-sulfolen-2-yl)decane-1-
Got the oars.

1HNMR(CDCta) δ(I)I)m) 1.00(aH,t, J=7.0
Hz) 8.20 (2H, t, J-6, 5Hz) ■ (1
Synthesis of 1E,13E,113E)-11,13-hexadecadienal 10-(6-ethyl-3-sulfolene-2-
300 ml of decane-1-ol was dissolved in 5 d of 95% ethanol, 280 ml of potassium carbonate was added thereto, and the mixture was heated to 13E)0°C for 1.5 hours in a sealed tube under an argon atmosphere.

Next, the reaction solution was cooled to room temperature, and ethyl acetate was added to it for 20 minutes.
After adding -, the inorganic salt was removed and the solvent was distilled off. The obtained residual liquid was subjected to column chromatography using 10 g of silica gel (eluent: ethyl acetate: n-hexane = 1:9) to obtain the desired (11E, 13E, 1aE).
-11,13-11,13-hexadecadienal 2B
(3v was obtained (yield: 95%).

'HNMR (CDCts) J (ppm) 1.05 (8H, t, J=s7.0H
z) 1.20 to 1.80 (161 (, m) 2.05 (4H, m) 2.68 (IH, b℃ 3) 8.60 (2H, t, J = 6.0H2) 5.60 (2
B, m) 6.00 (2H, m) 'CNMR (CDCLa) δ(1)pm) 113E). 78 82.67
13E) 2.36 29.561B0.44
29.28 129.55 25.86 62.71 25.61 82.78 13E). 68 M5 /z288(M) ■ Synthesis of (11E,13E,13E)-11,1B-hexadecadienal (11E,13E)-11, obtained as above,
13E)-Hexadecagenol 844 was dissolved in a mixed solvent of methylene chloride 1O- and n-hexane 10M and added to it by the method of D, Michelot et al.
pCC-alumina 8.56-F prepared according to Synthesis, 198L13E)0) was added, and the mixture was stirred at room temperature under an argon atmosphere for 10 hours. After treating the reaction solution in a conventional manner, the obtained crude product was subjected to column chromatography using silica gel 15N (eluent: ethyl acetate:n-hexane-1:9) to obtain the desired product (11E, 1
3E, 1flIE)-11,1ill-11,13-hexadecadienal was obtained at 26°Ov (yield: 67.
2%).

[HNMR(CDCLa) δ(riI)m) 1.00(ill)(, t, J=7
．． 0Hz) 1.20-1.50 (12H, m) 1.60 (2H, m) 2.06 (4H, m) 2.44 (2H, dt, J=2.0Hz.

J=8.0Hz) 5.60(2H,m) 6.03(2B,m) 9.82(if(,t, J=2.0f(Z)13CNM
R δ(pI)m) 202.15 82.591
3E) B, 48 29. 41128.98 13E). 5048.88 IR(CH(:t3) 1720 an 'MS
” / 286 (M) Reference Example 1 Synthesis of 0-tetrahydropyranyloxydecyl iodide 1. Mix 201 of 10-decanediol and 100% of 57% hydroiodic acid, add 500.d of toluene, and add 600.d of toluene.
The resulting 10-hydroxydecyl iodide is continuously extracted while heating under reflux for a period of time. The mixture is then cooled to room temperature, the precipitated 1,10-decanediol is removed, and the toluene layer is washed successively with an aqueous IN-potassium carbonate solution, Heide and saturated brine, and the toluene is distilled off under reduced pressure. The residue was distilled in the presence of potassium carbonate and heated to 85-87°C/0.
25.081 of 10-hydroxydecyl iodide was obtained as a colorless oil as a fraction of I Torr.

Next, 11.6 g of the iodide was converted to the corresponding tetrahydropyranyl ether by a conventional dry chlorination method, and the resulting crude product was subjected to silica gel column chromatography (eluent: n-hexane: ethyl acetate - 9:1). , 14.89 of the desired 10-tetrahydrobyranyloxydecyl iodide was obtained (yield: 98%).

1HNMR (CDC6s) δ (reduction rate 84 (22H, m) 8.20 (2H,t, J-6,5Hz) 8.6
0 (4H, m) 4.60 (IH, m) (16 complete)

Claims (3)

[Claims] (1) By heating 10-(5-ethyl-3-sulfolen-2-yl)decane-1-ol in the presence of an alkali, (11E,13E)-11,13-hexadecadien-1- (11E,13E)-11, which is characterized by leading to ol, and then oxidizing the hydroxyl group of the compound.
, 13-hexadecadienal production method. (2) 2-(10-tetrahydropyraniloxydecyl)
- Treating 5-ethyl-3-sulfolene with an acid to lead to 10-(5-ethyl-3-sulfolene-2-yl)decane-1-ol, and then heating the compound in the presence of an alkali. By (11E, 13E)-11,
13-hexadecadien-1-ol, and then oxidizes the hydroxyl group of the compound (11E,
13E) Method for producing -11,13-hexadecadienal. (3) 2-(10
-tetrahydropyranyloxydecyl)-5-ethyl-3
- Treating sulfolene with an acid leads to 10-(5-ethyl-3-sulfolen-2-yl)decane-1-ol, and then heating the compound in the presence of an alkali (11E, 13E). )-11,13-hexadecadien-1-ol, and then oxidizing the hydroxyl group of the compound.