JPS5925385A - (2s or 2r,1's)-(4'-oxa-2'-cyclohexenyl)-3-buten-1-ol - Google Patents

Abstract

NEW MATERIAL:(2S,1'S)-(4'-Oxa-2'-cyclohexenyl)-3-buten-1-ol of formula I and (2R,1'S)-(4'-oxa-2'-cyclohexenyl)-3buten-1-ol of formula II. USE:Useful as an intermediate for biosynthesis of corynanthe type indole alkaloids, e.g. corynanthidine or corynantheidine, capable of exhibiting the activity as a drug for the digestive organ system, particularly the gastrointestinal system. PROCESS:Ice water is added to a dried whole herb of a commercially available Japanese green gentian, and the herb is crushed in a blender to form a slurry, which is then steam distilled to give a distillate. The resultant distillate is then saturated with common salt and extracted repeatedly twice with ether. The solvent is then distilled away under reduced pressure to give an essential oil of the Japanese green gentian, which is purified to give the compounds of formulas I and II.

Description

Detailed Description of the Invention The present invention provides a novel compound represented by the following structural formula [1] or [2], (2S or 2R,1'S ) -(4'-oxa-2'-cyclohexenyl) -3-Buten-1-ol also relates.

,,,,OH+. ,,□'1" Traditionally, many useful compounds have been synthesized for use in medicines, fragrances, food additives, etc.However, recently, due to consideration of their effects on the human body, compounds that do not exist in nature have been synthesized. There is a tendency for natural compounds that have been used for a long time to be preferred over completely artificial compounds. japonica Mak
As a result of intensive research, we have completed the present invention.

The compound according to the present invention is represented by the structural formula [1] (2
s, I'5)-(4'-oxa-27-cyclohexenyl)-13-buten-1-ol and (2R,1's) to (4'-oxa -27-cyclohexenyl)-3-buten-1-ol, which is a completely novel compound whose structure was first isolated and determined by the present inventors.

Compounds of the present invention include corinatidine, corinateidin, etc.
It can be a very useful intermediate in the biosynthesis of corinanthe type indole alkaloids.
030) One of the aroma components (4S or 4
R) 4-ethynyl-2,8-dioxabicyclo(3,3
, 1) Nonane is obtained by cyclizing the compound of the present invention with P-toluenesulfonic acid, etc. These compounds are expected to have effective pharmacological activity on the digestive system, especially the gastrointestinal system. be.

Next, a specific method for producing the compound of the present invention will be described.

Add ice water to 5 kg of commercially available dried whole plant Assemblage (Japanese Pharmacopoeia Assemblage), crush it in a blender, turn it into a slurry, and steam-distill it. The distillate was saturated with sodium chloride, extracted twice with ether, and then the solvent was pressure-sensitively distilled off to obtain 1.5 g of essential oil of Aspergillus orientalis. This essential oil was subjected to column chromatography using 80 g of silica gel and sequentially eluted with the following solvents.

1. Hexa7 500 mg2.
5% ether/hexane 3 Fl 0 m13
．． 10% ether/hexane 300 me4.
15% ether/hexane 300 ml115.
30% ether/hexane 300 ml Of this, the eluate of 30% ether/hexane (300 rnl) was collected and the solvent was distilled off under reduced pressure to yield 258.7 ml/J.
essential oil components were obtained. This accounts for 17.2% of the total amount of essential oil.

Furthermore, by repeatedly fffing this fraction using a silica gel Rover column, two types of alcohols [1] (
Micrometer), (2) (2,0 m9) was obtained.

The properties of these compounds are shown below.

Compound [1) (2S, 1'5)-(4'-oxa-
2'-Cyclohexenyl)-3-buten-1-ol Properties: Colorless oil Molecular weight: 154 (0OH1402)λ(S(Vz,
%): 39 (13), 55 (49), 83 (
100), 91 ('7), 154 (4) Compound (2) (2R,1'S) -(4'-oxa-2'
-Cyclohegysenyl)-3-butene-1-ol Form: Colorless oil Molecule't: 154 (C!9Ht40z)MS
(m/”'St%) ' 39 (36')l 5
J (53) + 83 (100) 91 (7), 99 (
7), 109 (11), 136 (41°154 (2) I R (neat film): 340 (] (OH),
3050°1630.905 (C=OH2>cm'H
-NMR (360MHz, δI71)m, C6D6)6
．． 39 (LH, ad, , T=2.0.6.5), 5
．． 40 (IH, aaa, J=8.9.10.2.17
．． 0).

4.9'7 (LH, clda, :f=0.7.2.0
．． 10.2).

4.87 (IH, aaa, J=1.0.2.0.17
．． 0).

4.47 (IH, aat, J=0.8.3.2.6.
5).

3.74 (IH, aaa, J=4.5.5.0.10
．． 5).

3.66 (IH, dad, , T=5.0.5.5.1
0.5).

3.49 (IH, brddd, J==4.5.10.
5).

3.30 (LH, a, a, :r=7.5.10.5)
, 2.00 (IH, complex), 1.86
(LH, tda, J=5.0.8.0.8.0),
1.42(2H,complexm)+”-8(L
Hlm)

Claims (1)

[Claims] Represented by the following structural formula [1] or [2] (2B or 2
R,1'S) -(4'-,oxa-2'-cyclohexenyl)-3-buten-1-ol4 Material 0H・N0H・