CN1094719A - novel optically active compound and preparation method thereof - Google Patents
novel optically active compound and preparation method thereof Download PDFInfo
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- CN1094719A CN1094719A CN 93118657 CN93118657A CN1094719A CN 1094719 A CN1094719 A CN 1094719A CN 93118657 CN93118657 CN 93118657 CN 93118657 A CN93118657 A CN 93118657A CN 1094719 A CN1094719 A CN 1094719A
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Abstract
The present invention relates to novel formula (I) compound and preparation method thereof.Make diimidazole ketone and formula ∴ (R wherein
1Be CH
3, CF
3, R
2Be phenyl, benzyl etc., Y is NH
2, OH etc.) the compound reaction can make formula (I) compound.
Formula of the present invention (I) compound has multi-functional group (multirole group; MRG) effect; as: light influential action alive, hydrotropy effect, blocking group effect split group and the effect of indication group; it is organic synthesis; be useful reagent in the asymmetric synthesis, be particularly suitable for being used for complete synthesis optically active false bufotoxin amidoalcohol that has.Also can be used to synthetic other and have optically active compound.
Description
The present invention relates to optically active compound of a kind of novelty and preparation method thereof, particularly relate to the down N-S-(-of formula I)-Orazamide compounds that 1-replaces and preparation method thereof.
Complete synthesisly have in optically active false bufotoxin amidoalcohol procedure in research, the inventor once puted forth effort to seek and a kind ofly can play the live reagent of influential action of light, so that synthesize the inequality enantiomorph of false bufotoxin amidoalcohol.But after the literature search of strictness, do not find ideal reagent like that.Pier Cvorgio Cozzi etc. are at Tetrahadron Letters the 31st volume; No. 39 5661～5664 pages of (1990) Nian Zhongyong tertbutyloxycarbonyls (BOC) are as blocking group; Miguel O.Mitchell etc. are at Tetrahedron Letters the 31st volume; then make the trifluoroacetyl derivative in 2681～2684 pages No. 19; but these groups all have only provide protection and unglazed influential action alive is racemic form so finally synthesize the false bufotoxin amidoalcohol product.
Has optically active product in order to synthesize easily; people wish to have a class reagent; it had both had light influential action alive; make it in tetrahedral asymmetric synthesis, have stereoselectivity; and certain the part group in the reagent also can be used as blocking group; this group also has the function of " indication group " in case of necessity; help people in nuclear magnetic resonance technique, to determine the ratio of enantiomer and diastereomer; and as rolling over the fractionation group that divides mapping and diastereomer plays multiple effect in reaction process group, i.e. multi-functional group.（MRG，multi-role group）
An object of the present invention is to provide a kind of compound of novelty; it both can be used as chemical reaction reagent; making organic synthesis have that stereoselectivity, group wherein 2 can be used as blocking group, index group and be the fractionation group of enantiomer and diastereomer, is a kind of reagent with multi-function action group.
Another object of the present invention provides the preparation method of this compounds.
The compounds of this invention has the structure of formula I:
R in the formula
*Can be general chiral radicals, preferably example be (
):
The solid line of using in the formula (
) be meant the substituting group that is positioned at paper plane top, dotted line (...) be meant the substituting group that is positioned at paper plane below; Ph represents phenyl, and Naph represents naphthyl.
Compound of the present invention can be prepared by following method
A) make down formula II 1,1 '-diimidazole ketone and formula III compound react,
R in the formula III
1Expression CH
3Or CF
3;
R
2Expression phenyl, naphthyl, cyclohexyl and pyridyl;
Y represents NH
2Or OH.
Thereby made the formula I compound
B) make formula II 1,1 '-diimidazole ketone and formula IV compound react.
R wherein
1, R
2, Y definition the same,
Made the formula I compound.
R wherein
*For
Above-mentioned reaction all can be carried out in organic solvent in room temperature to the reflux temperature of solvent, 1 minute～48 hours reaction times.
Described organic solvent is normal hexane, anhydrous acetyl, hexanaphthene, dehydrated alcohol, anhydrous methanol, tetrahydrofuran (THF), dioxane, methane dioxide, chloroform benzene, toluene acetonitrile or their mixed solvent.
Below we the invention will be further elaborated in conjunction with most preferred embodiment.
Embodiment 1
Preparation
(N-S-(-)-1-styroyl imidazoles-1-methane amide)
With 1 equivalent 1,1 '-the diimidazole ketone is dissolved in the 100ml tetrahydrofuran (THF), add 1 equivalent S-(-at ambient temperature)-the 1-phenylethylamine, stir after 20 minutes,, use anhydrous magnesium sulfate drying with tetrahydrofuran (THF) extraction four times 120 * 4ml), boil off solvent, ethyl acetate: methylene dichloride makes residue through quick silica gel column chromatography chromatography purification at 95: 5, obtain colourless, the title compound of oily matter.
Yield: 95%
[α]
23 D＝-6.7（C＝0.9CHCl
3）
HNMR（CDCl
3，200MHz）
ppm 1.62（d，3H，CH
3），5.10～5.24（m，1H CHCH
3），694（s，1H），7.30～7.45（m，6H），8.05（s，1M）.
Embodiment 2
Preparation
With 2 equivalents 1,1 '-the diimidazole ketone is dissolved in the 200ml tetrahydrofuran (THF), adds 2 equivalent R-(+ after the stirring and dissolving)-the 1-naphthalene ethylamine, be heated to 40 ℃, stirring reaction was used chloroform extraction 4 times (50 * 4ml) after 50 minutes, behind anhydrous sodium sulfate drying, boil off solvent, obtain raw product.This product obtains the pure product of solid of white through quick silica gel column chromatography chromatography purification (making elutriant with acetone).
HNMR（200MH
2z，CDCl
3）1.67（d，2H），5.5（m，1H），6.9（s，1H），7.2-8.2（m，9H）.
Compound of the present invention can be successfully used in the asymmetric synthesis, R wherein
*Chiral radicals has blocking group simultaneously, instructs the effect that splits mapping and diastereomer in the indication group effect isolation technique in three-dimensional selective action, the spectroscopic techniques.And the hydrotropy effect of the solubleness of assisted reaction thing in toluene, be the real class novel agents that belongs in the organic synthesis of reagent with multi-functional group; In addition, because compound of the present invention is easy to synthesize, therefore the yield height helps the widespread use of The compounds of this invention in asymmetric organic synthesis.
Claims (9)
1, a kind of compound is characterized in that it has the structure of following formula I:
R wherein
*Expression chiral carbon group.
2, compound according to claim 1 is characterized in that wherein R
*Be
Chiral radicals.
3, compound according to claim 1 and 2 is characterized in that this compound is N-S-(-)-1-styroyl imidazoles-1-methane amide.
4, a kind of method of formula I compound down for preparing:
R wherein
*Expression chiral carbon group
It is characterized in that this method comprises:
A) make down formula II, 1,1 '-diimidazole ketone and formula III compound react
R wherein
1Expression CH
3Or CF
3;
R
2Expression phenyl, naphthyl, cyclohexyl and pyridyl;
Y represents NH
2Or OH;
B) make formula II, 1,1 '-diimidazole ketone and formula IV compound react:
R wherein
1, R
2The same with the definition of Y
5, method according to claim 4 is characterized in that wherein R
*Be
Chiral radicals.
6, method according to claim 4 is characterized in that this method carries out in organic solvent.
7, method according to claim 6 is characterized in that wherein said organic solvent is to be selected from the group of being made up of normal hexane, anhydrous diethyl ether, hexanaphthene, dehydrated alcohol, anhydrous methanol, tetrahydrofuran (THF), dioxane, methylene dichloride, chloroform, acetonitrile, benzene, toluene and their mixed solvent.
8, method according to claim 4, it is characterized in that this temperature of reaction at-40 ℃ to the scope of the reflux temperature of solvent.
9,, it is characterized in that this method has made N-S-(-according to claim 4 or 6 or 7 described methods)-1-styroyl imidazoles-1-methane amide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93118657A CN1048485C (en) | 1992-09-30 | 1993-09-29 | Optical active compound and preparing process thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108584 CN1070640A (en) | 1992-09-30 | 1992-09-30 | The preparation method of novel optically active compound |
| CN92108584.2 | 1992-09-30 | ||
| CN93118657A CN1048485C (en) | 1992-09-30 | 1993-09-29 | Optical active compound and preparing process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1094719A true CN1094719A (en) | 1994-11-09 |
| CN1048485C CN1048485C (en) | 2000-01-19 |
Family
ID=25742780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93118657A Expired - Fee Related CN1048485C (en) | 1992-09-30 | 1993-09-29 | Optical active compound and preparing process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1048485C (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59141562A (en) * | 1983-02-01 | 1984-08-14 | Nippon Kayaku Co Ltd | N,n'-substituted imidazolecarboxamide derivative and agricultural and horticultural germicide and nematocide |
| JPS59181260A (en) * | 1983-03-30 | 1984-10-15 | Sumitomo Chem Co Ltd | Preparation of optically active imidazole derivative |
| DE3513259A1 (en) * | 1985-04-13 | 1986-10-23 | Bayer Ag, 5090 Leverkusen | HETEROCYCLIC AMID DERIVATIVES |
| JPS62238272A (en) * | 1986-04-09 | 1987-10-19 | Otsuka Chem Co Ltd | Imidazolecarboxylic acid ester derivative, production thereof and plant growth regulator and herbicide containing said derivative as active ingredient |
| EP0429186A1 (en) * | 1989-11-21 | 1991-05-29 | Ube Industries, Ltd. | Imidazole derivative, preparation thereof and fungicide |
-
1993
- 1993-09-29 CN CN93118657A patent/CN1048485C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1048485C (en) | 2000-01-19 |
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