JPS58157734A - (2r,3s)-octanediol and its derivative - Google Patents

Abstract

NEW MATERIAL:(2R,3S)-Octanediol of formulaI(R is H, alkyl, alkylidine, acyl) and its derivatives. USE:An attractant of female bate (Xylotrechus pyrrhoderus), a harmful insect to grape. PREPARATION:Ethyl D-lactate is prepared from D-alanine through D-lactic acid nand made to react with dry ammonia to give D-lactic acid amide. Then, a Grigard reagent prepared from 1-bromopentane is made to the amide to give (2R,3S)- octanediol. Further, when necessary, the product is made to react with dimethoxypropane to give (4R,5S)-2,2,4-trimethyl-5-n-amyl-1,3-dioxolane.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to (2R,3E+)-octanediol, which is a novel compound represented by the following formula [1], and derivatives thereof.

ROl, 0R II U3n11, Ums
Here, R each represents an H1 alkyl group, an alkylidine group, or an acyl group.

In our research on methods for exterminating grape pests, the present inventors found that (2B, 3s)-octanediol has an attractive effect on female grape vipers,
The present invention was achieved as a result of synthesizing various analogous compounds thereof and studying their ability to attract female grape cutworms.

The compounds of the present invention are novel compounds synthesized for the first time by the present inventors, and the structural formulas and physical properties of a few representative compounds are as follows.

(1) (2R+ 3 s )-octanediol H
Shishi 770H Optical rotation: (t) 28'-12,0° IR: 3350cIIL'H-NM, R (CDcx3.100MH2): δ0
．． 90 (3H, t.

J:6H2), 1.14 (3H, d, J Near H2)
).

3.60 (IH, m), 3.77 (IH, m) 130-
NMR: 20H3 (14,0,16,5), 4cn2
(19,4°22.5.25.7.31.8), 2-
0H-0(70,4°74.9) (2) (4R,5s)-2,2,4-)dimethyl-
5-n-amyl-1,3-dioxolane H3CH3 \/ Optical rotation't: (:t)P 5,9° (0HQI3.
Concentration 1i-0,70"4)'H-NMR (0Dcl8
．． 100MHz): δ0.89 (3H, t.

J=6Hz), 1.14(3H, (1, J=6H2),
1.35 (3H, 8) 11.44 (3E, S), 4.0
3 (IH.

aa, J=4.12Hz), 4.26(IH, aa
, y=6.12Hz) 130-NMR: 40H3(14,0,15,6,2
5, 9, 28, 6).

40H2 (22, 6, 25, 9, 29, 7, 31, 9)
, 2-0H-0(73,8,78,2),0(10
7,2) Furthermore, these compounds have an excellent ability to attract female grape beetles even when they fall down.

Next, specific methods for synthesizing these compounds will be described.

(1) Synthesis of (2R,28)-octanediol. 25
．． Dissolve D-alanine (No. 9) in 300 d of water, and add 23.6 g of sodium nitrite to this aqueous solution while stirring.
A solution of 70 d of water and 170 ml of 2N sulfuric acid were added dropwise in equal amounts over 2 hours. Continue stirring and leave overnight.

The reaction mixture was concentrated under reduced pressure, the remaining inorganic salt was extracted with hot acetone, and the solvent was distilled off under reduced pressure to obtain 16.6 g of D-lactic acid.

Add the same amount of benzene to this mixture, add a small amount of concentrated sulfuric acid, attach a trap, and heat to reflux to remove the water produced. After heating for 4 hours, ethanol was added, the mixture was further refluxed, and the ethanol and benzene were removed under reduced pressure. This was then purified by distillation to obtain 16.6 g of ethyl D-lactate.

The above-obtained lactic acid ethyl ester e was placed in a flask containing 200 g/dry NH3 gas at room temperature for 28 hours.

The resulting ethanol was then removed under reduced pressure to obtain 11.1 g of fiD-lactic acid amide.

Place 15 g of Mp shavings in a 500-shoulder 4-bottle flask and pour in anhydrous ether, then add 1-pentane bromide 8
A solution of 0.5 g dissolved in 100 g of ether was added dropwise over 2 hours. After the metal Mg is completely melted, 1 more
After refluxing for a period of time, 8.9 g of the above L-lactic acid amide was added at 30 r.
Add ul of ether in 10 minutes. Reflux for an additional 4 hours. After cooling, the reaction mixture is poured into ice water, and concentrated hydrochloric acid is added until the aqueous layer becomes transparent.

The aqueous layer was saturated with salt, and after extraction with ether, the extract was
Wash with IJum and dry with sodium sulfate. The solvent was distilled off under reduced pressure and the residue was dissolved in 100 d of methanol. Then 2.37g of borohydride)
Add IJum to the solution and stir for 4 hours, then acidify with concentrated hydrochloric acid. Add 300111 ether to this solution and wash with brine. This washing liquid is also extracted with ether. Ether solution (5% carbonic acid, washed with IJum, sulfuric acid)
Dry with IJum. After distilling off the solvent, the residue was purified by silica gel column chromatography to obtain a mixture of 2R, 3B octanediol and 21,3R octanediol in a yield of 24% from ethyl D-lactate.

This mixture was dissolved in a small amount of ether, added with an equal amount of pentane, crystallized, and cooled to obtain 2R,3S octanediol as colorless needle crystals with a purity of 95%.

(2) (4R,58)-2,2,4-)rifutyl-3-
In the middle cylinder of the n-amyl-1,3-dioxolanthus extractor, there is a
4A) and put Penzea 50tt1 into the lower flask.
1 (2R,28)-octanediol 2,og,P-
) 121 ng of luenesulfonic acid and 2.4 gi of 2゜2-dimethoxypropane were added, and the mixture was refluxed for about 3 hours.

After cooling to room temperature, anhydrous potassium carbonate was added and stirred to neutralize, and the solvent was distilled off under reduced pressure. The residue was dissolved in ethyl and diluted with 10% aqueous carbonate).The mixture was washed with an aqueous solution of IJ and then with water, and the ether was distilled off under reduced pressure to give (4R,58)-2゜2 as a colorless oil. .4-trimethyl-3-
2.4 g of n-amyl-1,3-dioxolane was obtained.

2371

Claims (1)

[Scope of Claims] (2R,3s)-octanediol and its derivatives RO·, , ·OR represented by the following formula, where R each represents an H1 alkyl group, an alkylidine group, or an acyl group.