CN101024621A - 2-nitro-benzoyl-imino-acenaphthylene derivative compound and use thereof - Google Patents
2-nitro-benzoyl-imino-acenaphthylene derivative compound and use thereof Download PDFInfo
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Abstract
The invention relates to a dinitrobenzene formacyl imdo group acenaphthene derivatization compound that has the structure of general expression (I). And R1 represents hydrogen, C1-C3 is alkyl, R2 is alkylidene group, alkenyl, and R3 expresses one-hydrogen or two-hydrogen. After taking acylation reaction of arene, alpha-H replacing reaction of ketone, and reduction amination of ketone carbonyl, and acylation reaction of amine acyl halide, the product would be gained. The invention also relates to the single antipode of the compound, including chiral reagent or chiral additive. It could be used as chiral reagent in film method and chiral stationary phase or chiral mobile phase.
Description
Technical field
The invention belongs to acenaphthene derivative compound and uses thereof technical field, be specifically related to a kind of new 2-nitro-benzoyl-imino-acenaphthylene derivative compound and the purposes of this compound.
Background technology
Along with further developing of life science and medicine and pharmacology, people find that gradually the chirality enantiomer of medicine exists at aspects such as pharmacology, toxicity and clinical efficacies than big-difference, as present use one of medicine NSAID (non-steroidal anti-inflammatory drug) Naproxen Base comparatively widely, its S (left-handed) type single chiral compound is just than 28 times of the strong drug actions of R (dextrorotation) type single chiral compound.Because most of new drug all will be a chiral drug in this century, thereby, the resolving chiral enantiomer of drugs is not only the needs of analyzing its purity, is that the prepared in laboratory chiral drug supplies pharmacology, toxicity and clinical study needs, also is to carry out the needs that suitability for industrialized production provides commodity to use.
At present in the research and development process of various chirality things especially chiral drug, be prefered method with the method for the direct resolving chiral enantiomorph of liquid chromatography principle, this class methods key in application is to need suitable chiral stationary phase.The functional mass of chiral stationary phase is chipal compounds or chirality candidate.Existing many so far various chiral stationary phases or chirality candidate are open, but that really can be employed is few [the Eric R.Francotte of number, Journal ofChromatographyA, 906,379-397 (2001)], its one of the main reasons is to split effect to be unsatisfied with, and it is generally very limited to be suitable for the scope that splits object.In addition, the raw material for preparing these chirality things is mostly more expensive, and synthesis step is long again, causes cost high.
Pirkle (William H.Pirkle and Thomas C.Pochapsky.Considerations of chiral recognitionrelevant to the liquid chromatographic separation of enantiomers.Chem.Rev.1989,89:347-362) proposed in the design of brush property hand-type stationary phase, to have the principle of great importance: adverse effect principle (theprinciple ofreciprocity) each other, if promptly one of enantiomorph of a fixed compd A can carry out chiral separationization between the enantiomorph of another compd B, vice versa so.According to this principle, Pirkle study group has successively prepared (3 of π acid type, the 5-dinitrophenyl) (R)-the DNB derivative CSP (DNB-PG CSP) of phenylglycine and (3, the 5-dinitrophenyl) (R)-leucic DNB derivative CSP (DNB-Leucine CSP).Owing to only contain the acidic aromatic group in this two kinds of chiral stationary phases (CSP) candidate structure, thereby it is better to split effect for the enantiomorph that contains basic group, then can not split sometimes for the enantiomorph that contains acidic-group.
Main researchist of the present invention once designed and had synthesized π-alkali type amides brush type chiral stationary phase SH-1CSP (ZL02133368.8), formula as follows, but its split result shows that this CSP is bad to the fractionation effect that contains alkaline aromatic group in most of tested drug molecules.Trace it to its cause, the one, because in the interaction force between drug molecule and the CSP, π between aromatic ring-πDian Zi interacts and is still the isolating prerequisite of enantio-selectivity, and the testing drug molecule can not form effective π-π effect with CSP, causes being split.The 2nd, the space structure around the chiral carbon atom on the SH-1 CSP is good inadequately, and medicine from a plurality of locus and CSP absorption, causes and can not be split easily.
Summary of the invention
The objective of the invention is problem, a kind of new acenaphthene derivative compound---2-nitro-benzoyl-imino-acenaphthylene derivative compound is provided at the prior art existence.
Another object of the present invention provides a kind of single chiral compound of above-mentioned acenaphthene derivative compound.
A further object of the present invention provides the purposes of above-mentioned acenaphthene derived single chiral compound.
New acenaphthene derivative compound provided by the invention---2-nitro-benzoyl-imino-acenaphthylene derivative compound, its structure can be represented with following general formula (I):
R wherein
1Expression hydrogen, C
1～C
3Alkyl; R
2Expression alkylidene group, alkenyl; R
3Represent a hydrogen or two hydrogen.
Above-mentioned R
1The C of expression
1～C
3Alkyl be meant the straight or branched alkyl with 1～3 carbon atom, for example methyl, ethyl, propyl group, sec.-propyl.
Above-mentioned R
2The alkylidene group of expression preferably has the alkylidene group of the straight or branched of 2～9 carbon atoms, for example ethylidene, propylidene, isopropylidene, inferior normal-butyl, isobutylidene, pentylidene, hexylidene, inferior nonyl etc.
Above-mentioned R
2The alkenyl of expression preferably has the alkenyl of the straight or branched of 2～10 carbon atoms, for example vinyl, butenyl, isopentene group, nonene base etc.
Preferred especially R
1Expression hydrogen, R
2Expression C
4～C
10Alkenyl or C
2～C
3Alkylidene group, R
3Represent a hydrogen or two hydrogen.
Above-mentioned acenaphthene derivative compound provided by the invention is that the acenaphthene with cheapness is main starting raw material; obtain through the steps such as acylation reaction of reduction amination, amine and the carboxylic acid halides of the friedel-crafts acylation of aromatic hydrocarbons, the α of ketone-H substitution reaction, ketone carbonyl, its compound structure is confirmed by 1HNMR.
Above-claimed cpd provided by the invention, as be split into single enantiomer or the chirality thing can directly be used for the resolving chiral enantiomorph as chiral reagent, maybe the single enantiomer of this compound is connected with mould material and makes the chiral separation film and be used for the resolving chiral enantiomorph, perhaps with the silica gel bonded chiral stationary phase of making phase chromatography-use that is connected.
The single chiral compound of above-mentioned acenaphthene derivative compound provided by the invention is that the acenaphthene derivative compound that will be obtained splits with suitable method, as it being split with preparative columns such as DNB-Leucine chiral stationary phases, just can obtain the single enantiomer S and the R type chirality thing of this compound, its chiral carbon atom C
*Expression is shown in (II).
R wherein
1, R
2, R
3The group of representative and above-mentioned identical, slightly.
R in formula (II)
3During for H, can be further and silica gel bonded S provided by the invention or the R type chipal compounds stationary phase of being connected to form, its general formula (III) is:
In the formula (III), R
4Expression C
1～C
3Alkyl, C
1～C
3Alkoxyl group, for example methyl, ethyl, methoxyl group, oxyethyl group etc.
Provided by the invention have 3 of a said structure; the derive purposes of chipal compounds stationary phase of 5-dinitrobenzoyl imido grpup acenaphthene is to analyze and preparation resolving chiral enantiomer of drugs and pharmaceutical intermediate, is particularly useful for analyzing or prepares splitting the amide derivatives enantiomorph etc. that contains π tart amide derivatives enantiomorph and contain π alkalescence.
Compared with the prior art the present invention has the following advantages:
1, because acenaphthene derivative compound provided by the invention, be with cheap acenaphthene as main starting raw material, and synthetic, thereby cost is low with technology than conventional ripening.
2, because acenaphthene derivative compound synthesis step provided by the invention is shorter, synthetic route maturation, synthesis condition are easy to control, and be simple to operate, preparation that can be fairly large.
3, the single chiral compound of R or S type can not only be used for liquid-phase chromatography method resolving chiral enantiomorph as the chirality candidate because acenaphthene provided by the invention is derived, for example be used for chirality moving phase chromatography or chiral stationary phase chromatography method, also can directly be used for other method for splitting as chiral reagent, for example be used for chiral film partition method resolving chiral enantiomorph, thereby have wider purposes as chiral reagent.
4, the single chiral compound of R or S type because acenaphthene provided by the invention is derived, not only have π-acidity (band electron-withdrawing substituent) aromatic group near its chiral centre, the aromatic group that also has π-alkalescence (band pushes away electron substituent group), thereby π-π charge transfer interaction can take place in the chiral recognition process; Can form the atom or the group of hydrogen bond; Superimposed interactional polar link of dipole-dipole or group can take place; Can provide steric repulsion, Van der Waals to interact and (or) the bigger non-polar group of configuration control, when using the method for conventional ripening to be connected with silica gel, it makes chiral stationary phase cheaply, and this chiral stationary phase both can split π tart amide derivatives enantiomorph well, also can split the amide derivatives enantiomorph that contains π alkalescence well, thereby the chiral chromatography stationary phase that this chirality candidate is made has than existing commercialization chiral stationary phase for example DNB-Lucine and DNB-PG etc., has the scope of application widely.
5, the single chiral compound of R or S type because acenaphthene provided by the invention is derived, its chiral carbon atom side carbon chain lengths has reduced, thereby has improved the space structure around it, has further improved the recognition capability of its fractionation.
Embodiment
Embodiment given below is that the invention will be further described, is convenient to those skilled in the art and more fully understands the present invention.But given embodiment can not be interpreted as limiting the scope of the invention, thereby nonessential improvement and adjustment that this technical professional is made according to the invention described above content also should belong to protection domain of the present invention.
Embodiment 1
Present embodiment is 5-[1-(3,5-dinitrobenzoyl imines)-4-pentenyl]-preparation of acenaphthene compound and chirality thing thereof.
The synthetic 12.0g of the getting aluminum trichloride (anhydrous) of 5-ethanoyl acenaphthene (2) is dissolved in the 120ml methylene dichloride, adds the 4.4g Acetyl Chloride 98Min. in ice bath while stirring, adds 10.4g acenaphthene (1) at last.Remove ice bath, at room temperature react 25min, be about to previously prepd ice distilled water and pour into wherein with termination reaction.With saturated sodium carbonate solution and water washing, drying is revolved steaming.Ether/normal hexane=1: 3 (V: V) be solvent with the product recrystallization, obtain faint yellow solid powder (2), productive rate is 58%, fusing point is 67.0～68.5 ℃.
Synthetic 30ml benzene is packed into of 5-(4-alkene-pentanoyl)-acenaphthene (3) is warming up to 50 ℃ in the flask, adds 3.9g potassium tert.-butoxide powder and 4.2g bromopropylene; Other gets 35ml benzene and is warming up to 40 ℃, adds 6.0g product (2) dissolving, and this solution is splashed in the flask with sample injector, and the limit edged stirs; With mixture heating up to 95 ℃, backflow 3h, stopped reaction.After the reaction solution cooling, wash with water, drying is revolved steaming.Do column chromatography with toluene, remove raw material and by product, get reddish-brown crystal (3), productive rate is 24%, and fusing point is 76.0～78.0 ℃.
Synthesizing of 5-(1-amine-4-pentenoyl)-acenaphthene (4) adds 1.0g product (3), the dry boron sodium cyanide of 1.3g, the dry ammonium acetate of 3.3g, 10ml Virahol in stainless steel microreactor (about 20ml), mix; The airtight back of container is immersed in 110 ℃ of oil baths reaction 24h.After the cooling, the evaporative removal Virahol adds an amount of ether and water washing again, and drying vacuumizes and removes most of solvent, places crystallization, and the normal hexane washing obtains yellow crystals (4), and productive rate is 58%, and fusing point is 123.0～125.0 ℃.
5-[1-(3,5-dinitrobenzoyl imines)-4-pentenyl]-synthesizing of acenaphthene (5) product (4) 0.6g is dissolved in the 40ml methylene dichloride, and add excessive saturated sodium bicarbonate solution stirring; At 0.6g3, add methylene dichloride in the 5-dinitrobenzoyl chloride and dissolve, and pour violent stirring 2h in the solution that is added with product (4) into to it.After reacting end, filter, separatory, dehydration is filtered, and vacuumizes the removal solvent and gets orange/yellow solid.The gained solid is dissolved to fully with benzene and is heated to 40 ℃, add normal hexane while hot, when precipitation generates, i.e. cooling is filtered, and throw out washs with normal hexane.Carry out recrystallization with 85% ethanol, obtain white crystal (5), productive rate is 21%, and fusing point is 188.0～190.0 ℃.Product (5)
1HNMR data (CDCl
3, 200 MHz) and δ: 2.19～2.24 (m, 2H, CH
2), 2.34～2.37 (m, 2H, CH
2), 3.37～3.42 (m, 4H, C
5H
4), 5.02～5.06 (q, 1H, CH), 5.11～5.14 (q, 1H, CH), 5.23～5.27 (m, 1H, CH), 5.81～5.90 (m, 1H, CH), 5.99～6.08 (d, 1H, CH), 7.10～7.84[m, 5H, N (C
10H
5)], 8.91 (s, 2H, 2CH), 9.12 (s, 1H, CH).
R or S type chirality thing 5-[1-(3,5-dinitrobenzoyl imines)-4-pentenyl]-preparation of acenaphthene (6)
Present embodiment splits the racemic product (5) that is obtained with (L)-DNB-Leucine stationary phase chiral separation post.Chromatographic run condition: column temperature: 20.0 ℃, moving phase is Virahol: normal hexane=10: 90, detect wavelength X=254nm.
Above-mentioned whole process reaction equation is as follows:
Embodiment 2
Present embodiment is 5-[1-(3,5-dinitrobenzoyl imines)-10-undecylene acyl group] preparation of acenaphthene compound and chirality thing thereof.
Synthetic and the embodiment 1 of 5-ethanoyl acenaphthene (2) is identical, slightly.
Synthetic 30ml benzene is packed into of 5-(10-undecylene acyl group)-acenaphthene (3) is warming up to 50 ℃ in the flask, adds 3.9g potassium tert.-butoxide powder and 4.2g bromine ten carbon propylene; Other gets 40ml benzene and is warming up to 40 ℃, adds 6.0g product (2) dissolving, and this solution is splashed in the flask with sample injector, and the limit edged stirs; With mixture heating up to 95 ℃, backflow 3h, stopped reaction.After the reaction solution cooling, wash with water, drying is revolved steaming.Do column chromatography with toluene, remove raw material and by product, get reddish-brown crystal (3), productive rate is 24%.Fusing point is 113.0～115.0 ℃.
Synthesizing of 5-(1-amine-10-undecylene acyl group)-acenaphthene (4) adds 1.5g product (3), the dry boron sodium cyanide of 1.6g, the dry ammonium acetate of 4.5g, 20ml Virahol in stainless steel reactor (about 40ml), mix; The airtight back of container is immersed in 110 ℃ of oil baths reaction 24h.After the cooling, the evaporative removal Virahol adds an amount of ether and water washing again, and drying vacuumizes and removes most of solvent, places crystallization, and the normal hexane washing obtains yellow crystals (4), and productive rate is 58%, and fusing point is 167.0～169.0 ℃.
5-[1-(3,5-dinitrobenzoyl imines)-10-undecylene acyl group]-synthesizing of acenaphthene (5) product (4) 0.9g is dissolved in the 40ml methylene dichloride, and add excessive saturated sodium bicarbonate solution stirring; At 0.9g3, add methylene dichloride in the 5-dinitrobenzoyl chloride and dissolve, and pour violent stirring 2 h in the solution that is added with product (4) into to it.After reacting end, filter, separatory, dehydration is filtered, and vacuumizes the removal solvent and gets orange/yellow solid.The gained solid is dissolved to fully with benzene and is heated to 40 ℃, add normal hexane while hot, when precipitation generates, i.e. cooling is filtered, and throw out washs with normal hexane.Carry out recrystallization with 85% ethanol, obtain white crystal (5), productive rate is 16%, and fusing point is 238～239 ℃.
R or S type chirality thing 5-[1-(3,5-dinitrobenzoyl imines)-10-undecylene acyl group]-preparation of acenaphthene (6)
Present embodiment is used (L) with the racemic product (5) that is obtained--and DNB--Leucine stationary phase chiral separation post splits.Chromatographic run condition: column temperature: 20.0 ℃, moving phase is Virahol: normal hexane=10: 90, detect wavelength X=254nm.
Above-mentioned whole process reaction equation is as follows:
Embodiment 3
Present embodiment is 5-[1-(3,5-dinitrobenzoyl imines)-4-amyl group]-preparation of acenaphthene compound and chirality thing thereof.
The synthetic 12.0g of the getting aluminum trichloride (anhydrous) of 5-ethanoyl acenaphthene (2) is dissolved in the 120ml methylene dichloride; in ice bath, add the 4.4g Acetyl Chloride 98Min. while stirring; add 10.4g acenaphthene (1) at last; remove ice bath; at room temperature react 25min, be about to previously prepd ice distilled water and pour into wherein with termination reaction.With saturated sodium carbonate solution and water washing, drying is revolved steaming.Ether/normal hexane=1: 3 (V: V) be solvent with the product recrystallization, obtain faint yellow solid powder (2), productive rate is 58%, fusing point is 69.0-71.0 ℃.
Synthetic 30ml benzene is packed into of 5-(4-alkene-amyl group)-acenaphthene (3) is warming up to 50 ℃ in the flask, adds 3.9g potassium tert.-butoxide powder and 4.2g N-PROPYLE BROMIDE; Other gets 35ml benzene and is warming up to 40 ℃, adds 6.0g product (2) dissolving, and this solution is splashed in the flask with sample injector, and the limit edged stirs; With mixture heating up to 95 ℃, backflow 3h, stopped reaction.After the reaction solution cooling, wash with water, drying is revolved steaming.Do column chromatography with toluene, remove raw material and by product, get reddish-brown crystal (3), productive rate is 24%, and fusing point is 79.0～81.0 ℃.
Synthesizing of 5-(1-amine-4-amyl group)-acenaphthene (4) adds 1.0g product (3), the dry boron sodium cyanide of 1.3g, the dry ammonium acetate of 3.3g, 10ml Virahol in stainless steel microreactor (about 20ml), mix; The airtight back of container is immersed in 110 ℃ of oil baths reaction 24h.After the cooling, the evaporative removal Virahol adds an amount of ether and water washing again, and drying vacuumizes and removes most of solvent, places crystallization, and the normal hexane washing obtains yellow crystals (4), and productive rate is 58%, and fusing point is 126.0～128.0 ℃.
5-[1-(3,5-dinitrobenzoyl imines)-4-amyl group]-synthesizing of acenaphthene (5) product (4) 0.6g is dissolved in the 40ml methylene dichloride, and add excessive saturated sodium bicarbonate solution stirring; At 0.6g3, add methylene dichloride in the 5-dinitrobenzoyl chloride and dissolve, and pour violent stirring 2h in the solution that is added with product (4) into to it.After reacting end, filter, separatory, dehydration is filtered, and vacuumizes the removal solvent and gets orange/yellow solid.The gained solid is dissolved to fully with benzene and is heated to 40 ℃, add normal hexane while hot, when precipitation generates, i.e. cooling is filtered, and throw out washs with normal hexane.Carry out recrystallization with 85% ethanol, obtain white crystal (5), productive rate is 21%, and fusing point is 194.0～196.0 ℃.
Above-mentioned whole process reaction equation is as follows:
Embodiment 4
Present embodiment is that explanation splits (the R)-leucic DNB (3 that contains the π acid type with the previous embodiment 1 prepared acenaphthene made chiral stationary phase chromatography method of chipal compounds (6) of deriving; the 5-dinitrophenyl) application examples of derivative enantiomorph (formula V as follows); and the application examples of the N-acidylate of π alkali type-1-arylamino alkane type chirality enantiomorph (formula VI as follows), have separate object more widely to prove this chiral stationary phase material.
Chiral stationary phase preparation obtains for example dimethylchlorosilane (CH of the R of material 6 or S type single chiral enantiomorph and alkyl silicon with embodiment 1 split back
3)
2SiHCl reacts bonding, and be connected in promptly get on the silica gel this 3, the chiral stationary phase of 5-2-nitro-benzoyl-imino-acenaphthylene derivative compound, its structural formula are formula (IV).
Chirality Separation of Enantiomers or fractionation present embodiment split the instrument that uses and are Waters515 type highly effective liquid phase chromatographic system.Chromatographic condition is: the moving phase Virahol: hexane=10: 90,20 ℃ of temperature, UV-detector wavelength X=254nm.
Use the chiral stationary phase method resolution of racemates material (V) of aforesaid method and (VI).Through the chromatographic column fractionation π-acid type amides chirality enantiomorph (V) is arranged, its separation factor 1.24, resolution are 2.50; Split π-alkali type amides chirality enantiomorph (VI), its separation factor 1.37, resolution are 1.52.And appearance time is shorter, in 10～15 minutes.As seen this chiral stationary phase has fruit of good fractionation for the material of π-acid and π-alkali type, and the scope of application is wider.
Claims (8)
1, a kind of 2-nitro-benzoyl-imino-acenaphthylene derivative compound, its structure can be represented with following general formula (I):
R wherein
1Expression hydrogen, C
1～C
3Alkyl; R
2Expression alkylidene group, alkenyl; R
3Represent a hydrogen or two hydrogen.
2, acenaphthene derivative compound according to claim 1 is characterized in that this chipal compounds is with chiral carbon atom C
*Be the center, respectively with acenaphthenyl, substituent R
1, R
2And with 3, the compound of R type that 5-dinitrobenzoyl imido grpup is constituted and S type single chiral enantiomer-specific structure, its general formula (II) is:
3, acenaphthene derivative compound according to claim 1 and 2 is characterized in that R
1Expression hydrogen.
4, acenaphthene derivative compound according to claim 1 and 2 is characterized in that R
2Expression C
2～C
9Alkylidene group, C
2～C
10Alkenyl, R
3Represent a hydrogen or two hydrogen.
5, acenaphthene derivative compound according to claim 1 and 2 is characterized in that R
2Expression C
4～C
10Alkenyl, R
3Represent a hydrogen.
6, acenaphthene derivative compound according to claim 1 and 2 is characterized in that R
2Expression C
2～C
3Alkylidene group, R
3Represent two hydrogen.
7, chipal compounds according to claim 2, one of its purposes are as chiral reagent or chiral additives, are used for membrane method resolving chiral enantiomorph.
8, chipal compounds according to claim 2, its another purposes are the chirality candidates as chromatography resolving chiral enantiomorph, and the form that this chirality candidate both can chiral stationary phase is used, and also can use with the form of chirality moving phase additive.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811034A (en) * | 2010-03-25 | 2010-08-25 | 王荣 | Synthesis and application of large-grain diameter chiral stationary phase |
| CN106242978A (en) * | 2016-07-28 | 2016-12-21 | 南京工业大学 | Method for preparing antioxidant 6PPD by using micro-reaction device |
| CN114618457A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Binitryl-substituted phenyl chromatographic stationary phase and preparation and application thereof |
-
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811034A (en) * | 2010-03-25 | 2010-08-25 | 王荣 | Synthesis and application of large-grain diameter chiral stationary phase |
| CN101811034B (en) * | 2010-03-25 | 2011-11-09 | 王荣 | Synthesis and application of large-grain diameter chiral stationary phase |
| CN106242978A (en) * | 2016-07-28 | 2016-12-21 | 南京工业大学 | Method for preparing antioxidant 6PPD by using micro-reaction device |
| CN106242978B (en) * | 2016-07-28 | 2018-08-31 | 南京工业大学 | Method for preparing antioxidant 6PPD by using micro-reaction device |
| CN114618457A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Binitryl-substituted phenyl chromatographic stationary phase and preparation and application thereof |
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