CN104003924B - N-replaces-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds and preparation method and application - Google Patents
N-replaces-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds and preparation method and application Download PDFInfo
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- CN104003924B CN104003924B CN201410230403.5A CN201410230403A CN104003924B CN 104003924 B CN104003924 B CN 104003924B CN 201410230403 A CN201410230403 A CN 201410230403A CN 104003924 B CN104003924 B CN 104003924B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/38—2-Pyrrolones
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
Abstract
The invention discloses <i>N</iGreatT.Gr eaT.GT-and replace-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds and preparation method and application, belong to organic synthesis and technical field of pesticide, its compound structure general formula is as (<b>I</bGreatT.Gr eaT.GT), invention describes with substituted aniline, ethyl chloroacetate, methyl aceto acetate, substituted benzaldehyde is raw material, synthesize a series of <i>N</iGreatT.Gr eaT.GT-and replace-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-pyrroline-2-one compounds.This compounds has good resisting tobacco mosaic virus live body therapeutic activity, can be used for preparing Antiphytoviral agricultural chemicals.
Description
Technical field
The present invention relates to the compound with Antiphytoviral and plant epiphyte, specifically
nthe preparation method of-replacement-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds and application.
Background technology
Pyrrolines is the important heterogeneous ring compound of a class, have sterilization, weeding, desinsection, except mite and agricultural chemicals and the medicinal activity such as antitumor, anti-infective.Isosorbide-5-Nitrae-pentadiene-3-ketone compounds is a kind of curcumin analogue, has agricultural chemicals and the medicinal activities such as plant epiphyte resisting, Antiphytoviral, anticancer, anti-inflammatory, anti-oxidant, AntiHIV1 RT activity.Therefore, be that natural skeleton is introduced Isosorbide-5-Nitrae-pentadiene-3-ketone structure and carried out further exploitation and have very wide prospect with pyrrolines.
1993, (Addor, the R.W. such as Addor; Donovan, S.F.; DIehl, R.E.
n-AcylatedArylpyrrolesUsefulasInsectIcIdalAgents [P].
uS5328928.,
1993.) report and synthesized compound
n-acidylate pyrrole derivatives.Show that this compounds has excellent pesticide and miticide actility by biological activity test, this compounds is 10 in concentration
μduring g/mL to southern mythimna separata (
spodopteraeIdanIa), Heliothis virescens (
helIothIsvIrescens) third-instar larvae, western potato leaf hopper (
empoascaabrupta) and Esterase B1 Gene strain tetranychid (
t.urtIcae) lethality rate all reach 100%, to cucumber 11 asterophyllite first (
dIabrotIcundecImpunctatahowawdI) and blattaria (
blattellagermanIca) also there is good inhibit activities.
2007, Zhu have congruence (Zhu Youquan, department learn triumphant, Zou little Mao, Liu Bin, Yang Huazheng. synthesis and the weeding activity of novel 3-hydroxy methylene tetramethyleneimine-2,4-derovatives are studied [J].
organic chemistry.,
2007, 27 (3): 355-390.).Report novel 3-hydroxy methylene tetramethyleneimine-2,4-dione compounds, with sulphur humulone for contrast medicament, carry out weeding activity test by rape Plating and barnyard grass small-radius curve track to this compounds, test result shows, this compounds has good weeding activity.
2011, Zhou Bing etc. (Zhou Bing, Yan little Hong, Peng Feng, Guo Nianmei, Zhong Juan, Yin Shuaiwen. the bacteriostatic activity [J] of alternaria alternata metabolite.
university Of Agriculture and Forestry In Fujian's journal (natural science edition).,
201140 (4): 416-420.) reporting alternaric bacteria methyl aceto acetate phase metabolite and have certain restraining effect to gibberella saubinetii, rice blast fungus, Sclerotinia sclerotiorum, tobacco ash arrhizus bacteria and dothiorella gregaria bacterium 5 kind of plant pathogenic fungi, is 800 in concentration
μduring g/mL, 38.11%, 76.35%, 47.81%, 60.24%, 57.24% is respectively to the inhibiting rate of 5 kinds of fungies.Contrast medicament derosal is 800 in concentration
μduring g/mL, 100%, 81.16%, 78.96%, 72.76%, 94.82% is respectively to the inhibiting rate of 5 kinds of fungies.Result shows that alternaric bacteria methyl aceto acetate phase metabolite has good inhibit activities to rice blast fungus.
2003, (ReksohadIprodjo, the M.S. such as ReksohadIprodjo; TImmerman, H.; SardjIman, S.S.DerIvatIvesofbenzylIdenecyclohexanone, benzylIdenecyclopentanone, andbenzylIdeneacetone, andtherapeutIcusesthereof [P].
uS0092772A.,
2003) synthesize serial substituted-phenyl-Isosorbide-5-Nitrae-pentadiene-3-ketone and cyclopentanone, pimelinketone analogue, and under 10,20,40 and 80mg/kg dosage, treat white mouse claw edema, to judge the antiphlogistic activity of each compound.Result of study shows, this compounds has good activity, ED
50being worth minimum is 20mg/kg, compound to staphylococcus aureus (
staphyloccocusaureusRosenbach), streptococcus pneumoniae (
streptococcuspneumonIae), Ko subtilis (
bacIllussubtIlIs), Candida albicans (
canIdIaalbIcans) etc. there is good restraining effect, wherein compound is 0.05 to the minimum inhibition concentration of staphylococcus aureus
μmol/L.
2004, (Youssef, the K.M. such as Yousse; El-Sherbeny; El-ShafIle, M.A.SynthesIsofcurcumInanaloguesaspotentIalantIoxIdant, cancerhemopreventIveagents [J].
arch.Pharm.Med.Chem.,
2004, 337:42-54.) and report 7 serial curcumin derivates, find that compounds exhibit goes out the activity removing trinitro-free radical between phenylbenzene preferably, inhibiting rate is 91.24% ~ 99.85%.In addition, compound is the safest to periphery multinuclear neutrophilic granulocyte, and survival rate is to 91%.
2006, (RamalIngan, the C. such as RamalIngan; Park, Y.T.; KabIlan, S.SynthesIs, stereochemIstryandantImIcrobIalevaluatIonofsubstItutedpI perIdIn-4-oneoxImeethers [J].
eur.J.Med.Chem.,
2006, 41 (6): 683-696.) report compound 2,6-diphenyl-piperidine-4-ketoxime ether compound, carried out antibacterial, antimicrobial and anti-mycotic activity test to this compounds, test result shows, compound to Bacillus subtilus (
bacIllussubtIlIs) show good inhibit activities, its minimum inhibition concentration (MIC) and control drug Streptomycin sulphate (
streptomycIn) close.Compound to flavus (
aspergIllusflavus) and candidiasis-51 (
candIda-51) potential inhibit activities is shown.According to MIC data, the activity of compound and control drug amphotericin (
amphoterIcIn) close.
From background technology, pyrrolines have good sterilization, weeding, desinsection, except mite active; Isosorbide-5-Nitrae-pentadiene-3-ketone compounds sterilization, the biological activity such as anti-oxidant.But about with natural pyrroline for basic framework, introduces the Isosorbide-5-Nitrae-compound of pentadiene-3-ketone structure and there is no people at present and reported, and research report both at home and abroad about this compounds activity of resisting tobacco mosaic virus is also less.
Summary of the invention
The object of the invention is to the new pyrrole quinoline compounds containing Isosorbide-5-Nitrae-pentadiene-3-ketone structure of a series of novel structure of design and synthesis.This compounds for basic framework, three is introduced Isosorbide-5-Nitrae-pentadiene-3-ketone structure with natural pyrroline, has carried out synthetic method and the test of Antiphytoviral live body treatment prolection to this series compound.
The present invention,
n-replacing-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds, its general structure is as follows:
(
I)
Wherein R
1be 2,3-dichloro, 2-methoxyl group, 2,3-dimethoxys, 2-fluoro-4-bromine, 3-nitro, 4-methyl, 4-bromine, 2-fluorine, 3-bromine, the fluoro-6-chlorine of 2-, 4-fluorine, 3,4-dichloros, 2,6-dichloros, 2-chlorine, 4-chlorine, hydrogen;
R
2for 4-methyl, 3,4-dimethyl.
Synthetic compound is as follows:
| I1 | N-p-methylphenyl-3-[3-(2,3-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I2 | N-p-methylphenyl-3-[3-(2-p-methoxy-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I3 | N-p-methylphenyl-3-[3-(2,3-Dimethoxyphenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I4 | N-p-methylphenyl-3-[3-(the fluoro-4-bromophenyl of 2-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I5 | N-p-methylphenyl-3-[3-(3-nitrophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I6 | N-p-methylphenyl-3-[3-(4-aminomethyl phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I7 | N-p-methylphenyl-3-[3-(4-bromophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I8 | N-p-methylphenyl-3-[3-(2-fluorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I9 | N-p-methylphenyl-3-[3-(3-bromophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I10 | N-p-methylphenyl-3-[3-(the fluoro-6-chloro-phenyl-of 2-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I11 | N-p-methylphenyl-3-[3-(4-fluorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I12 | N-p-methylphenyl-3-[3-(3,4-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I13 | N-p-methylphenyl-3-[3-(2-6-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I14 | N-p-methylphenyl-3-[3-(2-chloro-phenyl-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I15 | N-p-methylphenyl-3-[3-(2,4 dichloro benzene base)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I16 | N-(3,4-3,5-dimethylphenyl)-3-[3-(4-chloro-phenyl-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I17 | N-(3,4-3,5-dimethylphenyl)-3-[3-(4-bromophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I18 | N-(3,4-3,5-dimethylphenyl)-3-[3-(2-fluorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I19 | N-(3,4-3,5-dimethylphenyl)-3-[3-(3,4-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I20 | N-(3,4-3,5-dimethylphenyl)-3-[3-(3-bromophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I21 | N-(3,4-3,5-dimethylphenyl)-3-[3-(the fluoro-4-bromophenyl of 2-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I22 | N-(3,4-3,5-dimethylphenyl)-3-(3-phenyl-2-alkene-1-ketone)-4-hydroxypyrrole quinoline-2 ketone |
| I23 | N-(3,4-3,5-dimethylphenyl)-3-[3-(2,3-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I24 | N-(3,4-3,5-dimethylphenyl)-3-[3-(3-nitrophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I25 | N-(3,4-3,5-dimethylphenyl)-3-[3-(the fluoro-6-chloro-phenyl-of 2-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I26 | N-(3,4-3,5-dimethylphenyl)-3-[3-(2,4 dichloro benzene base)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I27 | N-(3,4-3,5-dimethylphenyl)-3-[3-(4-fluorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I28 | N-(3,4-3,5-dimethylphenyl)-3-[3-(2,6-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I29 | N-(3,4-3,5-dimethylphenyl)-3-[3-(2-chloro-phenyl-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
| I30 | N-(3,4-3,5-dimethylphenyl)-3-[3-(2-p-methoxy-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2 ketone |
The application of compound of the present invention is to prepare the application in plant epiphyte resisting and plant virus medicine.
Above-mentioned indication refers to medicine for the preparation of resisting tobacco mosaic virus, fusarium graminearum, capsicum wilt bacterium, Valsa mali and medicament preparing the application in plant epiphyte resisting and plant virus medicine.
Of the present invention
nthe synthetic method of-replacement-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds is with substituted aniline, ethyl chloroacetate, methyl aceto acetate, substituted benzaldehyde is raw material, with ethanol, dimethylbenzene, methyl alcohol for solvent be substituted, closed loop, aldol reaction synthesis, its synthetic route is:
。
The present invention
nsynthesis step and the processing condition of-replacement-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds are:
The first step:
nthe preparation of-phenylglycine ethyl ester;
Add in there-necked flask substituted aniline, ethyl chloroacetate, 95% ethanol and sodium acetate, wherein mol ratio: substituted aniline: ethyl chloroacetate: sodium ethylate=1:1:1-1:1.2:1, every 5mmol substituted aniline adds the ethanol 10mL of 95%, reflux, TLC follows the tracks of reaction process, adds water after reaction terminates, then extract with benzene, combining extraction liquid, removal of solvent under reduced pressure obtains red-purple solid, with the white solid of dehydrated alcohol recrystallization
n-phenylglycine ethyl ester;
Second step:
nthe preparation of-replacement-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
Get substituted-phenyl glycine ethyl ester, methyl aceto acetate, dry dimethylbenzene joins in there-necked flask, at 125-130 DEG C of backflow 24h, wherein mol ratio: substituted-phenyl glycine ethyl ester: methyl aceto acetate=1:1-1:1.5, every 1.3mmol substituted-phenyl glycine ethyl ester adds the dry dimethylbenzene of 5ml, TLC follows the tracks of reaction process, normal temperature is cooled to after raw material reaction is complete, be Standard entertion concentration by 1.3mmol substituted-phenyl glycine ethyl ester be 1mol/L sodium methylate 15mL, 48h is stirred under normal temperature, TLC follows the tracks of reaction process, after reaction terminates, 20mL water is added in system, pH=2-3 is adjusted to 20% dilute hydrochloric acid, with 20mL dichloromethane extraction 3 times, combining extraction liquid, use saturated common salt water washing, collect organic phase and use anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, removal of solvent under reduced pressure obtains thick product.Thick product methylene dichloride and recrystallizing methanol obtain solid
n-replace-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone;
3rd step:
nthe preparation of-replacement-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone:
Take
n-replacement-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone, adds anhydrous methanol and 50%KOH joins in there-necked flask, every 2mmol
n-replacement-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone adds anhydrous methanol 20mL, 50%KOH2mL, and stirring at normal temperature 20 minutes, produces a large amount of White Flocculus, add substituted benzaldehyde, wherein mol ratio:
n-replace-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone: substituted benzaldehyde=1:5; connect prolong backflow 6-8h; TLC follows the tracks of reaction process; after reaction terminates, add 10mL water to system, be adjusted to pH=2-3 with 20% dilute hydrochloric acid; separate out a large amount of yellow solid; natural filtration collects solid, dry for standby, adopts column chromatography for separation to obtain target compound
n-replace-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
The present invention
n-replacing-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds to be easy to synthesis, cost is low.Design of the present invention meets the requirement of environmental friendliness and Green Chemistry; The compound of the inventive method synthesis can be used as resisting tobacco mosaic virus drug use.
By once embodiment, foregoing of the present invention is described in further detail.
Embodiment
Embodiment one,
n(compound number is-4-hydroxypyrrole quinoline-2-ketone-p-methylphenyl-3-[3-(2,3-dichlorophenyl)-2-alkene-1-ketone]
i1) preparation.
The first step:
nthe preparation of-p-methylphenyl glycine ethyl ester:
Para-totuidine 0.55g (5mmoL) is added, ethyl chloroacetate 0.73g (6mmol), the ethanol 10mL of 95%, 0.49g (5mmol) sodium acetate in the there-necked flask of 50mL.Reflux 6h, add 20mL water after reaction terminates, then extract 3 times, combining extraction liquid with 20mL benzene, removal of solvent under reduced pressure obtains red-purple solid, obtains white solid with dehydrated alcohol recrystallization
n-p-methylphenyl glycine ethyl ester;
Second step:
nthe preparation of-p-methylphenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone:
Get
n-p-methylphenyl glycine ethyl ester 1g (1.3mmol), methyl aceto acetate 0.28g (1.9mmol), 5mL is dry, and dimethylbenzene joins in there-necked flask, normal temperature is cooled to after 125-130 DEG C of backflow 24h, add 15mL sodium methylate (1mol/L), under normal temperature, stir 48h.After reaction terminates, add 20mL water in system, the dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction 3 times, combining extraction liquid, uses saturated common salt water washing, collect organic phase and use anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, removal of solvent under reduced pressure obtains thick product.Thick product CH
3oH:CHCl
3=3:1 (volume ratio) recrystallization obtains compound
n-p-methylphenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone;
3rd step:
nthe preparation of-p-methylphenyl-3-[3-(2,3-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone:
Take
n-p-methylphenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone 500mg (2mmol), measure 20mL anhydrous methanol, 2mL50%KOH joins in there-necked flask, stirring at normal temperature 20mIn, produce a large amount of White Flocculus, add 10mmol2, 3-dichlorobenzaldehyde, connect prolong backflow 6-8h, TLC follows the tracks of reaction process, after reaction terminates, 10mL water is added to system, dilute hydrochloric acid with 20% regulates pH=2-3, separate out a large amount of yellow solid, natural filtration collects solid, dry for standby, adopt column chromatography for separation (methylene dichloride: triethylamine=250:1) (volume ratio), precipitation, add water, dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction three times, combining extraction liquid, removal of solvent under reduced pressure obtains target compound
n-p-methylphenyl-3-[3-(2,3-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Embodiment two,
n(compound number is-4-hydroxypyrrole quinoline-2-ketone-p-methylphenyl-3-[3-(2-p-methoxy-phenyl)-2-alkene-1-ketone]
i2) preparation.
The first step:
nthe preparation of-p-methylphenyl glycine ethyl ester.
Para-totuidine 0.55g (5mmoL) is added, ethyl chloroacetate 0.73g (6mmol), the ethanol 10mL of 95%, 0.49g (5mmol) sodium acetate in the there-necked flask of 50mL.Reflux 6h, add 20mL water after reaction terminates, then extract 3 times, combining extraction liquid with 20mL benzene, removal of solvent under reduced pressure obtains red-purple solid, obtains white solid with dehydrated alcohol recrystallization
n-p-methylphenyl glycine ethyl ester.
Second step:
nthe preparation of-p-methylphenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
Get
n-p-methylphenyl glycine ethyl ester 1g (1.3mmol), methyl aceto acetate 0.28g (1.9mmol), 5mL is dry, and dimethylbenzene joins in there-necked flask, normal temperature is cooled to after 125-130 DEG C of backflow 24h, add 15mL sodium methylate (1mol/L), under normal temperature, stir 48h.After reaction terminates, add 20mL water in system, the dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction 3 times, combining extraction liquid, uses saturated common salt water washing, collect organic phase and use anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, removal of solvent under reduced pressure obtains thick product.Thick product CH
3oH:CHCl
3=3:1 (volume ratio) recrystallization obtains compound
n-p-methylphenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
3rd step:
nthe preparation of-p-methylphenyl-3-[3-(2-p-methoxy-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Take
n-p-methylphenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone 500mg (2mmol), measure 20mL anhydrous methanol, 2mL50%KOH joins in there-necked flask, stirring at normal temperature 20mIn, produce a large amount of White Flocculus, add 10mmol2-methoxybenzaldehyde, connect prolong backflow 6-8h, TLC follows the tracks of reaction process, after reaction terminates, 10mL water is added to system, dilute hydrochloric acid with 20% regulates pH=2-3, separate out a large amount of yellow solid, natural filtration collects solid, dry for standby, adopt column chromatography for separation (methylene dichloride: triethylamine=250:1) (volume ratio), precipitation, add water, dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction three times, combining extraction liquid, removal of solvent under reduced pressure obtains target compound
n-p-methylphenyl-3-[3-(2-p-methoxy-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Embodiment three,
n(compound number is-4-hydroxypyrrole quinoline-2-ketone-p-methylphenyl-3-[3-(2,6-dichlorophenyl)-2-alkene-1-ketone]
i13) preparation.
The first step:
nthe preparation of-p-methylphenyl glycine ethyl ester.
Para-totuidine 0.55g (5mmoL) is added, ethyl chloroacetate 0.73g (6mmol), the ethanol 10mL of 95%, 0.49g (5mmol) sodium acetate in the there-necked flask of 50mL.Reflux 6h, add 20mL water after reaction terminates, then extract 3 times, combining extraction liquid with 20mL benzene, removal of solvent under reduced pressure obtains red-purple solid, obtains white solid with dehydrated alcohol recrystallization
n-p-methylphenyl glycine ethyl ester.
Second step:
nthe preparation of-p-methylphenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
Get
n-p-methylphenyl glycine ethyl ester 1g (1.3mmol), methyl aceto acetate 0.28g (1.9mmol), 5mL is dry, and dimethylbenzene joins in there-necked flask, normal temperature is cooled to after 125-130 DEG C of backflow 24h, add 15mL sodium methylate (1mol/L), under normal temperature, stir 48h.After reaction terminates, add 20mL water in system, the dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction 3 times, combining extraction liquid, uses saturated common salt water washing, collect organic phase and use anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, removal of solvent under reduced pressure obtains thick product.Thick product CH
3oH:CHCl
3=3:1 (volume ratio) recrystallization obtains compound
n-p-methylphenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
3rd step:
nthe preparation of-p-methylphenyl-3-[3-(2,6-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Take
n-p-methylphenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone 500mg (2mmol), measure 20mL anhydrous methanol, 2mL50%KOH joins in there-necked flask, stirring at normal temperature 20mIn, produce a large amount of White Flocculus, add 10mmol2, 6-dichlorobenzaldehyde, connect prolong backflow 6-8h, TLC follows the tracks of reaction process, after reaction terminates, 10mL water is added to system, dilute hydrochloric acid with 20% regulates pH=2-3, separate out a large amount of yellow solid, natural filtration collects solid, dry for standby, adopt column chromatography for separation (methylene dichloride: triethylamine=250:1) (volume ratio), precipitation, add water, dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction three times, combining extraction liquid, removal of solvent under reduced pressure obtains target compound
n-p-methylphenyl-3-[3-(2,6-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Embodiment four,
n(compound number is-4-hydroxypyrrole quinoline-2-ketone-p-methylphenyl-3-[3-(2,4 dichloro benzene base)-2-alkene-1-ketone]
i15) preparation.
The first step:
nthe preparation of-p-methylphenyl glycine ethyl ester.
Para-totuidine 0.55g (5mmoL) is added, ethyl chloroacetate 0.73g (6mmol), the ethanol 10mL of 95%, 0.49g (5mmol) sodium acetate in the there-necked flask of 50mL.Reflux 6h, add 20mL water after reaction terminates, then extract 3 times, combining extraction liquid with 20mL benzene, removal of solvent under reduced pressure obtains red-purple solid, obtains white solid with dehydrated alcohol recrystallization
n-p-methylphenyl glycine ethyl ester.
Second step:
nthe preparation of-p-methylphenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
Get
n-p-methylphenyl glycine ethyl ester 1g (1.3mmol), methyl aceto acetate 0.28g (1.9mmol), 5mL is dry, and dimethylbenzene joins in there-necked flask, normal temperature is cooled to after 125-130 DEG C of backflow 24h, add 15mL sodium methylate (1mol/L), under normal temperature, stir 48h.After reaction terminates, add 20mL water in system, the dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction 3 times, combining extraction liquid, uses saturated common salt water washing, collect organic phase and use anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, removal of solvent under reduced pressure obtains thick product.Thick product CH
3oH:CHCl
3=3:1 (volume ratio) recrystallization obtains compound
n-p-methylphenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
3rd step:
nthe preparation of-p-methylphenyl-3-[3-(2,4 dichloro benzene base)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Take
n-p-methylphenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone 500mg (2mmol), measure 20mL anhydrous methanol, 2mL50%KOH joins in there-necked flask, stirring at normal temperature 20mIn, produce a large amount of White Flocculus, add 10mmol2, 4-dichlorobenzaldehyde, connect prolong backflow 6-8h, TLC follows the tracks of reaction process, after reaction terminates, 10mL water is added to system, dilute hydrochloric acid with 20% regulates pH=2-3, separate out a large amount of yellow solid, natural filtration collects solid, dry for standby, adopt column chromatography for separation (methylene dichloride: triethylamine=250:1) (volume ratio), precipitation, add water, dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction three times, combining extraction liquid, removal of solvent under reduced pressure obtains target compound
n-p-methylphenyl-3-[3-(2,4 dichloro benzene base)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Embodiment five,
n(compound number is-4-hydroxypyrrole quinoline-2-ketone-(3,4-3,5-dimethylphenyl)-3-[3-(4-chloro-phenyl-)-2-alkene-1-ketone]
i16) preparation.
The first step:
nthe preparation of-(3,4-3,5-dimethylphenyl) glycine ethyl ester.
Add in the there-necked flask of 50mL 3,4-xylidine 0.63g (5mmoL), ethyl chloroacetate 0.735g (6mmol), the ethanol 10mL of 95%, 0.492g (5mmol) sodium acetate.Reflux 6h, add 20mL water after reaction terminates, then extract 3 times, combining extraction liquid with 20mL benzene, removal of solvent under reduced pressure obtains red-purple solid, obtains white solid with dehydrated alcohol recrystallization
n-(3,4-3,5-dimethylphenyl) glycine ethyl ester.
Second step:
nthe preparation of-(3,4-dimethyl) phenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
Get
n-(3,4-3,5-dimethylphenyl) glycine ethyl ester 1g (1.2mmol), methyl aceto acetate 0.28g (1.9mmol), 5mL is dry, and dimethylbenzene joins in there-necked flask, normal temperature is cooled to after 125-130 DEG C of backflow 24h, add 15mL sodium methylate (1mol/L), under normal temperature, stir 48h.After reaction terminates, add 20mL water in system, the dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction 3 times, combining extraction liquid, uses saturated common salt water washing, collect organic phase and use anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, removal of solvent under reduced pressure obtains thick product.Thick product CH
3oH:CHCl
3=3:1 (volume ratio) recrystallization obtains compound
n-(3,4-dimethyl) phenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
3rd step:
nthe preparation of-(3,4-3,5-dimethylphenyl)-3-[3-(4-chloro-phenyl-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Take
n-(3, 4-3,5-dimethylphenyl)-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone 500mg (1.9mmol), measure 20mL anhydrous methanol, 2mL50%KOH joins in there-necked flask, stirring at normal temperature 20mIn, produce a large amount of White Flocculus, add 10mmol4-chlorobenzaldehyde, connect prolong backflow 6-8h, TLC follows the tracks of reaction process, after reaction terminates, 10mL water is added to system, dilute hydrochloric acid with 20% regulates pH=2-3, separate out a large amount of yellow solid, natural filtration collects solid, dry for standby, adopt column chromatography for separation (methylene dichloride: triethylamine=250:1), precipitation, add water, dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction three times, combining extraction liquid, the target compound of removal of solvent under reduced pressure
n-(3,4-3,5-dimethylphenyl)-3-[3-(4-chloro-phenyl-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Embodiment six,
n(compound number is-4-hydroxypyrrole quinoline-2-ketone-(3,4-3,5-dimethylphenyl)-3-[3-(4-bromophenyl)-2-alkene-1-ketone]
i17) preparation.
The first step:
nthe preparation of-(3,4-3,5-dimethylphenyl) glycine ethyl ester.
Add in the there-necked flask of 50mL 3,4-xylidine 0.63g (5mmoL), ethyl chloroacetate 0.735g (6mmol), the ethanol 10mL of 95%, 0.492g (5mmol) sodium acetate.Reflux 6h, add 20mL water after reaction terminates, then extract 3 times, combining extraction liquid with 20mL benzene, removal of solvent under reduced pressure obtains red-purple solid, obtains white solid with dehydrated alcohol recrystallization
n-(3,4-3,5-dimethylphenyl) glycine ethyl ester.
Second step:
nthe preparation of-(3,4-dimethyl) phenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
Get
n-(3,4-3,5-dimethylphenyl) glycine ethyl ester 1g (1.2mmol), methyl aceto acetate 0.28g (1.9mmol), 5mL is dry, and dimethylbenzene joins in there-necked flask, normal temperature is cooled to after 125-130 DEG C of backflow 24h, add 15mL sodium methylate (1mol/L), under normal temperature, stir 48h.After reaction terminates, add 20mL water in system, the dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction 3 times, combining extraction liquid, uses saturated common salt water washing, collect organic phase and use anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, removal of solvent under reduced pressure obtains thick product.Thick product CH
3oH:CHCl
3=3:1 (volume ratio) recrystallization obtains compound
n-(3,4-dimethyl) phenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
3rd step:
nthe preparation of-(3,4-3,5-dimethylphenyl)-3-[3-(4-bromophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Take
n-(3, 4-3,5-dimethylphenyl)-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone 500mg (1.9mmol), measure 20mL anhydrous methanol, 2mL50%KOH joins in there-necked flask, stirring at normal temperature 20mIn, produce a large amount of White Flocculus, add 10mmol4-bromobenzaldehyde, connect prolong backflow 6-8h, TLC follows the tracks of reaction process, after reaction terminates, 10mL water is added to system, dilute hydrochloric acid with 20% regulates pH=2-3, separate out a large amount of yellow solid, natural filtration collects solid, dry for standby, adopt column chromatography for separation (methylene dichloride: triethylamine=250:1), precipitation, add water, dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction three times, combining extraction liquid, the target compound of removal of solvent under reduced pressure
n-(3,4-3,5-dimethylphenyl)-3-[3-(4-bromophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Embodiment seven,
n(compound number is-4-hydroxypyrrole quinoline-2-ketone-(3,4-3,5-dimethylphenyl)-3-[3-(2-chloro-phenyl-)-2-alkene-1-ketone]
i29) preparation.
The first step:
nthe preparation of-(3,4-3,5-dimethylphenyl) glycine ethyl ester.
Add in the there-necked flask of 50mL 3,4-xylidine 0.63g (5mmoL), ethyl chloroacetate 0.735g (6mmol), the ethanol 10mL of 95%, 0.492g (5mmol) sodium acetate.Reflux 6h, add 20mL water after reaction terminates, then extract 3 times, combining extraction liquid with 20mL benzene, removal of solvent under reduced pressure obtains red-purple solid, obtains white solid with dehydrated alcohol recrystallization
n-(3,4-3,5-dimethylphenyl) glycine ethyl ester.
Second step:
nthe preparation of-(3,4-dimethyl) phenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
Get
n-(3,4-3,5-dimethylphenyl) glycine ethyl ester 1g (1.2mmol), methyl aceto acetate 0.28g (1.9mmol), 5mL is dry, and dimethylbenzene joins in there-necked flask, normal temperature is cooled to after 125-130 DEG C of backflow 24h, add 15mL sodium methylate (1mol/L), under normal temperature, stir 48h.After reaction terminates, add 20mL water in system, the dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction 3 times, combining extraction liquid, uses saturated common salt water washing, collect organic phase and use anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, removal of solvent under reduced pressure obtains thick product.Thick product CH
3oH:CHCl
3=3:1 (volume ratio) recrystallization obtains compound
n-(3,4-dimethyl) phenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
3rd step:
nthe preparation of-(3,4-3,5-dimethylphenyl)-3-[3-(2-chloro-phenyl-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Take
n-(3, 4-3,5-dimethylphenyl)-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone 500mg (1.9mmol), measure 20mL anhydrous methanol, 2mL50%KOH joins in there-necked flask, stirring at normal temperature 20mIn, produce a large amount of White Flocculus, add 10mmol2-chlorobenzaldehyde, connect prolong backflow 6-8h, TLC follows the tracks of reaction process, after reaction terminates, 10mL water is added to system, dilute hydrochloric acid with 20% regulates pH=2-3, separate out a large amount of yellow solid, natural filtration collects solid, dry for standby, adopt column chromatography for separation (methylene dichloride: triethylamine=250:1), precipitation, add water, dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction three times, combining extraction liquid, the target compound of removal of solvent under reduced pressure
n-(3,4-3,5-dimethylphenyl)-3-[3-(2-chloro-phenyl-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Embodiment eight,
n(compound number is-4-hydroxypyrrole quinoline-2-ketone-(3,4-3,5-dimethylphenyl)-3-[3-(2-p-methoxy-phenyl)-2-alkene-1-ketone]
i30) preparation.
The first step:
nthe preparation of-(3,4-3,5-dimethylphenyl) glycine ethyl ester.
Add in the there-necked flask of 50mL 3,4-xylidine 0.63g (5mmoL), ethyl chloroacetate 0.735g (6mmol), the ethanol 10mL of 95%, 0.492g (5mmol) sodium acetate.Reflux 6h, add 20mL water after reaction terminates, then extract 3 times, combining extraction liquid with 20mL benzene, removal of solvent under reduced pressure obtains red-purple solid, obtains white solid with dehydrated alcohol recrystallization
n-(3,4-3,5-dimethylphenyl) glycine ethyl ester.
Second step:
nthe preparation of-(3,4-dimethyl) phenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
Get
n-(3,4-3,5-dimethylphenyl) glycine ethyl ester 1g (1.2mmol), methyl aceto acetate 0.28g (1.9mmol), 5mL is dry, and dimethylbenzene joins in there-necked flask, normal temperature is cooled to after 125-130 DEG C of backflow 24h, add 15mL sodium methylate (1mol/L), under normal temperature, stir 48h.After reaction terminates, add 20mL water in system, the dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction 3 times, combining extraction liquid, uses saturated common salt water washing, collect organic phase and use anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, removal of solvent under reduced pressure obtains thick product.Thick product CH
3oH:CHCl
3=3:1 (volume ratio) recrystallization obtains compound
n-(3,4-dimethyl) phenyl-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone.
3rd step:
nthe preparation of-(3,4-3,5-dimethylphenyl)-3-[3-(2-p-methoxy-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
Take
n-(3, 4-3,5-dimethylphenyl)-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone 500mg (1.9mmol), measure 20mL anhydrous methanol, 2mL50%KOH joins in there-necked flask, stirring at normal temperature 20mIn, produce a large amount of White Flocculus, add 10mmol2-methoxybenzaldehyde, connect prolong backflow 6-8h, TLC follows the tracks of reaction process, after reaction terminates, 10mL water is added to system, dilute hydrochloric acid with 20% regulates pH=2-3, separate out a large amount of yellow solid, natural filtration collects solid, dry for standby, adopt column chromatography for separation (methylene dichloride: triethylamine=250:1), precipitation, add water, dilute hydrochloric acid with 20% regulates pH=2-3, with 20mL dichloromethane extraction three times, combining extraction liquid, the target compound of removal of solvent under reduced pressure
n-(3,4-3,5-dimethylphenyl)-3-[3-(2-p-methoxy-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
The synthesis of all the other compounds is similar to the above embodiments, does not enumerate at this.
Table 1 synthesizes
nthe structure of-replacement-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds
| Numbering | Product structure |
| I1 | |
| I2 | |
| I3 | |
| I4 | |
| I5 | |
| I6 | |
| I7 | |
| I8 | |
| I9 | |
| I10 | |
| I11 | |
| I12 | |
| I13 | |
| I14 | |
| I15 | |
| I16 | |
| I17 | |
| I18 | |
| I19 | |
| I20 | |
| I21 | |
| I22 | |
| I23 | |
| I24 | |
| I25 | |
| I26 | |
| I27 | |
| I28 | |
| I29 | |
| I30 |
Synthesis
nthe spectral data of-replacement-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compound.
n-p-methylphenyl-3-[3-(2,3-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i1)
Yellow solid, fusing point higher than 250 DEG C, yield: 52.5%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.34 (s, 3H, Ar-CH
3), 4.19 (s.2H, N-CH
2), 7.2 (d,
j=8.0Hz, 2H, Ar-H), 7.29 (d,
j=8.0Hz, 1H, Ar-H), 7.53 (d,
j=16.0Hz, 1H, Ar-CH=), 7.54 (t,
j=8.0Hz, 2H, Ar-H), 7.7 (d,
j=7.45Hz, 1H, Ar-H), 7.8 (d,
j=16Hz, 1H, Rr-CH=), 8.28 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 21.0,56.3,100.0,119.7,119.9,121.5,126.4,127.6,129.7,129.9,132.2,133.8,134.2,135.0,135.1,135.1,139.9,172.5,173.3,190.4.MS (ESI-MS): m/z=388.1 [M+H
+] .Anal.Calcd.ForC
20h
15cl
2nO
3: C, 61.84; H, 3.99; N, 3.66.Found:C, 61.87; H, 3.89; N, 3.61.
n-p-methylphenyl-3-[3-(2-p-methoxy-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i2)
Yellow solid, fusing point higher than 250 DEG C, yield: 52.5%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.34 (s, 3H, Ar-CH
3), 3.93 (s, 3H ,-OCH
3), 4.16 (s.2H, N-CH
2), 6.93 (d,
j=8.05Hz, 1H, Ar-H), 7.0 (d,
j=8.05Hz, 1H, Ar-H) 7.2 (d,
j=8.0Hz, 2H, Ar-H), 7.41 (t,
j=15.45Hz, 1H, Ar-H), 7.54 (t,
j=8.0Hz, 2H, Ar-H), 7.73 (d,
j=8.0Hz, 1H, Ar-H), 7.92 (d,
j=16.05Hz, 1H, Ar-CH=), 8.28 (d,
j=16.05Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 20.9,55.7,56.3,101.0,119.7,119.9,121.5,126.4,127.6,129.7,129.9,132.2,133.8,134.2,135.0,135.1,135.1,139.9,172.5,173.3,190.3.MS (ESI-MS): m/z=350.13 [M+H
+] .Anal.Calcd.ForC
21h
19nO
4: C, 72.00; H, 5.28; N, 3.98; Found:C, 72.19; H, 5.48, N, 4.01.
n-p-methylphenyl-3-[3-(2,3-Dimethoxyphenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i3)
Yellow solid, fusing point higher than 250 DEG C, yield: 56.5%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.34 (s, 3H, Ar-CH
3), 3.88 (s, 3H ,-OCH
3), 3.93 (s, 3H ,-OCH
3), 4.18 (s.2H, N-CH
2), 6.99 (d,
j=8.0Hz, 1H, Ar-H), 7.12 (t, 1H, Ar-H), 7.21 (d,
j=8.0Hz, 2H, Ar-H), 7.39 (d,
j=8.0Hz, 1H, Ar-H), 7.55 (d,
j=8.0Hz, 2H, Ar-H), 7.90 (d,
j=16.2Hz, 1H, Rr-CH=), 8.26 (d,
j=16.2Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 21.0,56.0,56.2,61.6,102.1,111.3,114.8.114.9,119.1,119.6,119.7,119.8,124.3,129.8,134.8,139.5,147.4,149.2,153.1,173.0,174.7,190.2.MS (ESI-MS): m/z=380.15 [M+H
+] .Anal.Calcd.ForC
22h
21nO
5: C, 69.58; H, 5.55; N, 3.84; Found:C, 69.64; H, 5.58, N, 3.69.
n-p-methylphenyl-3-[3-(the fluoro-4-bromophenyl of 2-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i4)
Yellow solid, fusing point higher than 250 DEG C, yield: 46.3%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.39 (s, 3H, Ar-CH
3), 4.18 (s.2H, N-CH
2), 6.99 (d,
j=8.0Hz, 1H, Ar-H), 7.21 (t, 2H, Ar-H) 7.24 (d,
j=8.0Hz, 2H, Ar-H), 7.55 (d,
j=8.0Hz, 2H, Ar-H), 7.58 (s, 1H, Ar-H), 7.82 (d,
j=16.0Hz, 1H, Rr-CH=), 7.90 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 21.7,56.2,101.9,117.3,119.6,120.1,120.3,129.2,129.3,129.7,129.9,131.5,131.9,134.8,135.3,142.1,145.1,173.1,174.7,190.3.MS (ESI-MS): m/z=453.6 [M+K
+] .Anal.Calcd.ForC
20h
15brFNO
3: C, 57.57; H, 3.65; N, 3.64; Found:C, 57.71; H, 3.63; N, 3.37.
n-p-methylphenyl-3-[3-(3-nitrophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i5)
Yellow solid, fusing point higher than 250 DEG C, yield: 34.3%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.39 (s, 3H, Ar-CH
3), 4.22 (s.2H, N-CH
2), 7.22 (d,
j=8.0Hz, 2H, Ar-H), 7.54 (d,
j=8.0Hz, 2H, Ar-H), 7.92 (t, 2H, Ar-H), 8.01 (d,
j=16.3Hz, 1H, Rr-CH=), 8.27 (d,
j=16.3Hz, 1H, CO-CH=) .8.46 (s, 1H, Ar-H).
13cNMR (500MHz, CDCl
3, ppm),
δ: 21.0,56.3,103.1,119.7,120.0,123.7,125.1,129.8,129.9,130.1,133.9,135.0,135.3,136.3,141.3,142.1,148.8,172.5,172.9,190.3.MS (ESI-MS): m/z=365.11 [M+H
+] .Anal.Calcd.ForC
20h
16n
2o
5: C, 65.86; H, 4.26; N, 7.83; Found:C, 65.93; H, 4.43; N, 7.69.
n-p-methylphenyl-3-[3-(4-aminomethyl phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i6)
Yellow solid, fusing point higher than 250 DEG C, yield: 33.6%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.34 (s, 3H, Ar-CH
3), 3.93 (s, 3H, Ar-CH
3), 4.27 (s.2H, N-CH
2), 7.13 (d,
j=8.0Hz, 2H, Ar-H), 7.21 (d,
j=8.0Hz, 2H, Ar-H), 7.54 (d,
j=8.0Hz, 2H, Ar-H), 7.57 (d,
j=7.8Hz, 2H, Ar-H), 7.91 (d,
j=16.0Hz, 1H, Rr-CH=), 8.18 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 21.1,46.9,56.3,103.1,119.7,120.0,123.7,125.2,129.8,129.9,130.1,133.9,135.0,135.3,136.7,141.1,142.1,148.8,172.4,172.7,190.4.MS (ESI-MS): m/z=334.15 [M+H
+] .Anal.Calcd.ForC
21h
19nO
3: C, 65.86; H, 4.26; N, 7.83; Found:C, 65.93; H, 4.43; N, 7.69.
n-p-methylphenyl-3-[3-(4-bromophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i7)
Yellow solid, fusing point higher than 250 DEG C, yield: 45.2%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.34 (s, 3H, Ar-CH
3), 4.18 (s.2H, N-CH
2), 7.13 (d,
j=8.0Hz, 2H, Ar-H), 7.21 (d,
j=8.0Hz, 2H, Ar-H), 7.51 (d,
j=8.0Hz, 2H, Ar-H), 7.53 (d,
j=8.0Hz, 2H, Ar-H), 7.54 (d,
j=8.0Hz, 2H, Ar-H), 7.56 (d,
j=7.7Hz, 2H, Ar-H), 7.81 (s, 2H, CH=CH),
13cNMR (500MHz, CDCl
3, ppm),
δ: 20.9,56.3,102.4,118.7,119.6,119.8,125.7,129.7,129.7129.9,129.9,130.3,132.4,133.5,135.0,135.2,143.3,172.8,173.9,190.3.MS (ESI-MS): m/z=398.1 [M+H
+] .Anal.Calcd.ForC
20h
16brNO
3: C, 60.42; H, 4.34; N, 3.61; Found:C, 60.32; H, 4.05, N, 3.52.
n-p-methylphenyl-3-[3-(2-fluorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i8)
Yellow solid, fusing point higher than 250 DEG C, yield: 53.2%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.35 (s, 3H, Ar-CH
3), 4.19 (s.2H, N-CH
2), 6.95 (t, 2H, Ar-H), 7.22 (d,
j=8.0Hz, 2H, Ar-H), 7.39 (t, 3H, Ar-H), 7.55 (d,
j=8.0Hz, 2H, Ar-H), 8.02 (d,
j=16.1Hz, 1H, Rr-CH=), 8.09 (d,
j=16.1Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 20.9,56.3,102.6,119.6,119.7,119.8,125.7,128.7,129.7,129.8,129.9,130.3,132.7,133.5,135.0,135.9,140.3,172.7,173.8,190.3.MS (ESI-MS): m/z=338.5 [M+H
+], 360.5 [M+Na
+] .Anal.Calcd.ForC
20h
16fNO
3: C, 71.75; H, 4.34; N, 4.25; Found:C, 71.21; H, 4.78; N, 4.15.
n-p-methylphenyl-3-[3-(3-bromophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i9)
Yellow solid, fusing point higher than 250 DEG C, yield: 65.2%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.35 (s, 3H, Ar-CH
3), 4.20 (s.2H, N-CH
2), 6.95 (t, 2H, Ar-H), 7.22 (d,
j=8.0Hz, 2H, Ar-H), 7.31 (t, 3H, Ar-H), 7.55 (d,
j=8.0Hz, 2H, Ar-H), 7.60 (s, 1H, Ar-H), 7.8 (d,
j=15.8Hz, 2H, CH=CH).
13cNMR (500MHz, CDCl
3, ppm),
δ: 21.1,56.3,102.1,119.7,120.2,123.7,125.1,129.8,129.9,130.3,133.9,135.0,135.3,136.3,141.3,142.1,148.8,172.4,172.9,190.7.MS (EMS): m/z=398.1 [M+H
+] .Anal.Calcd.ForC
20h
16brNO
3: C, 60.42; H, 4.34; N, 3.61; Found:C, 60.32; H, 4.05; N, 3.52.
n-p-methylphenyl-3-[3-(the fluoro-6-chloro-phenyl-of 2-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i10)
Yellow solid, fusing point higher than 250 DEG C, yield: 38.4%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.40 (s, 3H, Ar-CH
3), 4.20 (s.2H, N-CH
2), 7.19 (t, 1H, Ar-H), 7.23 (d,
j=8.0Hz, 2H, Ar-H), 7.40 (d,
j=7.6Hz, 2H, Ar-H), 7.54 (d.
j=8.0Hz, 2H, Ar-H), 8.04 (d,
j=15.6Hz, 1H, Rr-CH=), 8.07 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 21.1,56.2,103.2,119.6,126.3,126.6,129.2,129.5,129.9,131.4,131.8,130.3,132.1,132.3,135.4,135.6,137.7,172.6,173.2,190.3.MS (ESI-MS): m/z=416.1 [M+H
+] .Anal.Calcd.ForC
20h
15clFNO
3: C, 64.45; H, 3.98; N, 3.89; Found:C, 64.61; H, 4.07; N, 3.77.
n-p-methylphenyl-3-[3-(4-fluorophenyl)-2-alkene-1-ketone]-4-hydroxyl-pyrroline-2-one (compound
i11)
Yellow solid, fusing point higher than 250 DEG C, yield: 34.3%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.34 (s, 3H, Ar-CH
3), 4.16 (s.2H, N-CH
2), 6.94 (d,
j=7.6Hz, 2H, Ar-H), 7.20 (d,
j=8.0Hz, 2H, Ar-H), 7.55 (d,
j=8.0Hz, 2H, Ar-H), 7.64 (d,
j=8.0Hz, 2H, Ar-H), 7.73 (d,
j=16.0Hz, 1H, Rr-CH=), 7.91 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 20.9,56.2,101.3,114.7,115.6,119.5,119.7,127.4,128.8,129.7,129.8,131.1,131.3,134.7,135.4,144.9,162.4,173.2,174.8,190.3.MS (ESI-MS): m/z=338.3 [M+H
+] .Anal.Calcd.ForC
20h
16fNO
3: C, 72.22; H, 5.55; N, 4.15; Found:C, 71.21; H, 4.78; N, 4.15.
n-p-methylphenyl-3-[3-(3,4-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i12)
Yellow solid, fusing point higher than 250 DEG C, yield: 45.2%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.35 (s, 3H, Ar-CH
3), 4.20 (s.2H, N-CH
2), 7.22 (d,
j=8.0Hz, 2H, Ar-H), 7.50 (s, 1H, Ar-H), 7.55 (d,
j=8.0Hz, 2H, Ar-H), 7.73 (s, 2H, Ar-H), 7.77 (d,
j=15.6Hz, 1H, Rr-CH=), 7.79 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 21.0,56.3,101.9,117.1,119.6,123.5,129.2,129.3,129.6,129.9,131.7,132.4,134.6,134.8,135.2,142.1,145.1,173.2,174.7,190.1.MS (ESI-MS): m/z=388.6 [M+H
+] .Anal.Calcd.ForC
20h
15cl
2nO
3: C, 61.77; H, 4.10; N, 3.72; Found:C, 61.87; H, 3.89; N, 3.61.
n-p-methylphenyl-3-[3-(2,6-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i13)
Yellow solid, fusing point higher than 250 DEG C, yield: 38.4%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.35 (s, 3H, Ar-CH
3), 4.14 (s.2H, N-CH
2), 7.20 (t, 1H, Ar-H), 7.22 (d,
j=8.0Hz, 1H, Ar-H), 7.39 (d,
j=8.1Hz, 2H, Ar-H), 7.55 (d.
j=8.0Hz, 2H, Ar-H), 8.02 (d,
j=15.6Hz, 1H, Rr-CH=), 8.05 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm)
δ: 21.0,56.3,103.1,119.7,126.4,126.6,129.1,129.1,129.9,131.5,131.8,130.3,132.0,132.3,135.1,135.6,137.8,172.6,173.2,190.1.MS (ESI-MS): m/z=388.6 [M+H
+] .Anal.Calcd.ForC
20h
15cl
2nO
3: C, 61.89; H, 4.05; N, 3.71; Found:C, 61.87; H, 3.89; N, 3.61.
n-p-methylphenyl-3-[3-(2-chloro-phenyl-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i14)
Yellow solid, fusing point higher than 250 DEG C, yield: 65.2%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.34 (s, 3H, Ar-CH
3), 4.20 (s.2H, N-CH
2), 6.95 (t, 2H, Ar-H), 7.22 (d,
j=8.0Hz, 2H, Ar-H), 7.45 (t, 2H, Ar-H), 7.55 (d,
j=8.0Hz, 2H, Ar-H), 7.85 (d,
j=15.5Hz, 1H, Rr-CH=), 8.32 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 21.0,56.4,101.6,119.6,119.7,119.8,125.7,127.7,129.7129.8,129.9,131.3,132.7,133.5,135.0,135.9,140.3,172.6,173.8,191.1.MS (ESI-MS): m/z=354.08 [M+H
+] .Anal.Calcd.ForC
20h
16clNO
3: C, 67.78; H, 4.66; N, 3.60; Found:C, 67.90; H, 4.56; N, 3.96.
n-p-methylphenyl-3-[3-(2,4 dichloro benzene base)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i15)
Yellow solid, fusing point higher than 250 DEG C, yield: 55.3%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.35 (s, 3H, Ar-CH
3), 4.19 (s.2H, N-CH
2), 7.20 (d,
j=8.0Hz, 2H, Ar-H), 7.32 (d,
j=8.0Hz, 1H, Ar-H), 7.46 (s.1H, Ar-H), 7.55 (d,
j=8.0Hz, 2H, Ar-H), 7.79 (d,
j=8.0Hz, 1H, Ar-H), 7.83 (d,
j=16.0Hz, 1H, Rr-CH=), 8.21 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 20.9,56.4,101.8,117.2,119.5,123.4,129.1,129.4,129.5,129.8,131.6,132.3,134.5,134.5,135.5,142.1,145.3,173.2,174.5,190.2.MS (ESI-MS): m/z=388.6 [M+H
+] .Anal.Calcd.ForC
20h
15cl
2nO
3: C, 61.89; H, 4.05; N, 3.71; Found:C, 61.87; H, 3.89; N, 3.61.
n-(3,4-3,5-dimethylphenyl)-3-[3-(4-chloro-phenyl-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i16)
Yellow solid, fusing point higher than 250 DEG C, yield: 63.2%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.25 (s, 3H, Ar-CH
3), 2.29 (s, 3H, Ar-CH
3), 4.18 (s.2H, N-CH
2), 7.16 (d,
j=8.0Hz, 1H, Ar-H), 7.34 (d,
j=7.45Hz, 1H, Ar-H), 7.40 (d.
j=8.0Hz, 2H, Ar-H), 7.45 (s, 1H, Ar-H), 7.61 (d,
j=8.75Hz, 2H, Ar-H), 7.82 (s, 2H, CH=CH).
13cNMR (500MHz, CDCl
3, ppm),
δ: 19.3,20.2,56.4,102.4,117.2,118.7,121.1,129.4,129.4,130.2,130.4,130.3,133.1,133.8,135.4,137.2,137.7,143.1,172.8,173.9,190.4.MS (ESI-MS): m/z=368.3 [M+H
+] .Anal.Calcd.ForC
21h
18clNO
3: C, 68.56; H, 4.99; N, 3.82; Found:C, 68.57; H, 4.93; N, 3.81.
n-(3,4-3,5-dimethylphenyl)-3-[3-(4-bromophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i17)
Yellow solid, fusing point higher than 250 DEG C, yield: 48.8%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.25 (s, 3H, Ar-CH
3), 2.29 (s, 3H, Ar-CH
3), 4.18 (s.2H, N-CH
2), 7.16 (d,
j=8.0Hz, 1H, Ar-H), 7.34 (d,
j=8.0Hz, 1H, Ar-H), 7.45 (s, 1H, Ar-H), 7.56 (t, 4H, Ar-H), 7.82 (s, 2H, CH=CH
2).
13cNMR (500MHz, CDCl
3, ppm),
δ: 19.2,20.2,56.6,102.4,117.2,118.7,121.1,129.4,129.4,130.2,130.4,130.3,133.1,133.8,135.4,137.2,137.7,143.1,172.8,173.8,190.1.MS (ESI-MS): m/z=412.1 [M+H
+] .Anal.Calcd.ForC
21h
18brNO
3: C, 61.22; H, 4.53; N, 3.61; Found:C, 61.18; H, 4.40; N, 3.40.
n-(3,4-3,5-dimethylphenyl)-3-[3-(2-fluorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i18)
Yellow solid, fusing point higher than 250 DEG C, yield: 56.2%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.25 (s, 3H, Ar-CH
3), 2.29 (s, 3H, Ar-CH
3), 4.18 (s.2H, N-CH
2), 6.95 (t, 2H, Ar-H), 7.16 (d,
j=8.0Hz, 1H, Ar-H), 7.34 (d,
j=8.0Hz, 1H, Ar-H), 7.45 (s, 1H, Ar-H), 7.85 (d,
j=16.0Hz, 1H, Rr-CH=), 8.32 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 19.2,20.2,56.4,101.6,119.6,119.7,119.8,125.7,127.7,129.7129.8,129.9,131.3,132.7,133.5,135.0,135.9,140.3,172.6,173.8,191.1.MS (ESI-MS): m/z=352.1 [M+H
+] .Anal.Calcd.ForC
21h
18fNO
3: C, 71.12; H, 5.52; N, 4.22; Found:C, 71.78; H, 5.16; N, 3.99.
n-(3,4-3,5-dimethylphenyl)-3-[3-(3,4-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i19)
Yellow solid, fusing point higher than 250 DEG C, yield: 48.3%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.25 (s, 3H, Ar-CH
3), 2.29 (s, 3H, Ar-CH
3), 4.18 (s.2H, N-CH
2), 7.16 (d,
j=8.0Hz, 1H, Ar-H), 7.34 (d,
j=7.5Hz, 1H, Ar-H), 7.45 (t, 1H, Ar-H), 7.50 (s, 1H, Ar-H), 7.73 (s, 2H, Ar-H), 7.77 (d,
j=16.0Hz, 1H, Rr-CH=), 7.79 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 19.3,21.0,56.3,101.9,117.1,119.6,123.5,129.2,129.3,129.6,129.9,131.7,132.4,134.6,134.8,135.2,142.1,145.1,173.2,174.7,190.MS (ESI-MS): m/z=401.5 [M+H
+] .Anal.Calcd.ForC
21h
17cl
2nO
3: C, 62.58; H, 4.35; N, 3.64; Found:C, 62.70; H, 4.26; N, 3.48.
n-(3,4-3,5-dimethylphenyl)-3-[3-(3-bromophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i20)
Yellow solid, fusing point higher than 250 DEG C, yield: 37.5%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.25 (s, 3H, Ar-CH
3), 2.29 (s, 3H, Ar-CH
3), 4.19 (s.2H, N-CH
2), 7.14 (d,
j=8.0Hz, 1H, Ar-H), 7.31 (t, 3H, Ar-H), 7.33 (d,
j=8.0Hz, 1H, Ar-H), 7.45 (t, 1H, Ar-H), 7.60 (s, 1H, Ar-H), 7.8 (d,
j=15.7Hz, 2H, CH=CH).
13cNMR (500MHz, CDCl
3, ppm)
δ: 19.3,20.1,56.6,102.6,119.3,119.7,119.9,125.7,126.3,128.7129.8,129.9,131.3,132.5,133.5,135.0,165.9,140.3,172.5,173.5,190.3.MS (ESI-MS): m/z=412.1 [M+H
+] .Anal.Calcd.ForC
21h
18brNO
3: C, 60.90; H, 4.52; N, 3.46; Found:C, 61.18; H, 4.40; N, 3.40.
n-(3,4-3,5-dimethylphenyl)-3-[3-(the fluoro-4-bromophenyl of 2-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i21)
Yellow solid, fusing point higher than 250 DEG C, yield: 46.3%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.25 (s, 3H, Ar-CH
3), 2.29 (s, 3H, Ar-CH
3), 4.19 (s.2H, N-CH
2), 6.99 (d,
j=8.0Hz, 1H, Ar-H), 7.21 (t, 2H, Ar-H) 7.24 (d,
j=8.0Hz, 2H, Ar-H), 7.55 (d,
j=8.0Hz, 2H, Ar-H), 7.58 (s, 1H, Ar-H), 7.82 (d,
j=16.0Hz, 1H, Rr-CH=), 7.90 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 19.1,21.0,56.7,101.9,117.3,119.6,120.1,120.3,129.2,129.3,129.7,129.9,131.5,131.9,134.8,135.3,142.1,145.1,173.1,174.7,190.3.MS (ESI-MS): m/z=432.1 [M+H
+] .Anal.Calcd.ForC
21h
17brFNO
3: C, 58.94; H, 3.69; N, 3.35; Found:C, 58.62; H, 3.98; N, 3.26.
n-(3,4-3,5-dimethylphenyl)-3-(3-phenyl-2-alkene-1-ketone)-4-hydroxypyrrole quinoline-2-ketone (compound
i22)
Yellow solid, fusing point higher than 250 DEG C, yield: 45.3%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.25 (s, 3H, Ar-CH
3), 2.29 (s, 3H, Ar-CH
3), 4.19 (s.2H, N-CH
2), 7.16 (d,
j=8.0Hz, 1H, Ar-H), 7.34 (d,
j=7.6Hz, 2H, Ar-H), 7.43 (s, 2H, Ar-H), 7.46 (s, 1H, Ar-H), 7.68 (s.2H, Ar-H), 7.87 (d,
j=15.8Hz, 1H, Rr-CH=), 7.92 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 19.1,21.0,56.7,101.9,117.4,119.6,123.5,129.2,129.4,129.5,129.8,131.7,132.3,134.2,134.5,135.8,142.1,145.3,173.4,174.5,191.2.MS (ESI-MS): m/z=334.14 [M+H
+] .Anal.Calcd.ForC
21h
19nO
3: C, 75.58; H, 5.92; N, 4.15; Found:C, 75.66; H, 5.74; N, 4.20.
n-(3,4-3,5-dimethylphenyl)-3-[3-(2,3-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i23)
Yellow solid, fusing point higher than 250 DEG C, yield: 62.1%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.26 (s, 3H, Ar-CH
3), 2.30 (s, 3H, Ar-CH
3), 4.20 (s.2H, N-CH
2), 7.15 (d,
j=8.0Hz, 1H, Ar-H), 7.28 (t,
j=7.8Hz, 2H, Ar-H), 7.35 (d,
j=7.6Hz, 1H, Ar-H), 7.46 (s, 1H, Ar-H), 7.52 (d.
j=7.8Hz, 1H, Ar-H), 7.75 (d,
j=7.7Hz, 1H, Ar-H), 7.84 (d,
j=16.0Hz, 1H, Rr-CH=), 8.29 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 19.1,21.2,56.6,101.7,117.4,119.5,123.6,129.3,129.4,129.7,129.8,131.6,132.3,134.4,134.5,135.6,142.1,145.3,173.2,173.5,191.2.MS (ESI-MS): m/z=401.5 [M+H
+] .Anal.Calcd.ForC
21h
17cl
2nO
3: C, 62.83; H, 4.15; N, 3.31; Found:C, 62.70; H, 4.26; N, 3.48.
n-(3,4-3,5-dimethylphenyl)-3-[3-(3-nitrophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i24)
Yellow solid, fusing point higher than 250 DEG C, yield: 30.1%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.26 (s, 3H, Ar-CH
3), 2.30 (s, 3H, Ar-CH
3), 4.20 (s.2H, N-CH
2), 7.16 (d,
j=8.0Hz, 1H, Ar-H), 7.34 (d,
j=8.0Hz, 1H, Ar-H), 7.46 (d,
j=7.5Hz, 1H, Ar-H), 7.61 (d, 1H, Ar-H), 7.92 (t, 2H, Ar-H), 7.99 (d, 1H, Ar-H), 8.15 (d,
j=16.0Hz, 1H, Rr-CH=), 8.46 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 19.2,21.1,56.7,102.6,119.3,119.7,119.8,125.7,126.3,128.4129.8,129.9,131.3,132.4,133.5,135.0,165.7,140.3,172.3,173.5,191.1.MS (ESI-MS): m/z=368.1 [M+H
+] .Anal.Calcd.ForC
21h
18nO
3: C, 66.30; H, 5.05, N, 8.05; Found:C, 66.66; H, 4.79; N, 7.40.
n-(3,4-3,5-dimethylphenyl)-3-[3-(the fluoro-6-chloro-phenyl-of 2-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i25)
Yellow solid, fusing point higher than 250 DEG C, yield: 58.5%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.25 (s, 3H, Ar-CH
3), 2.29 (s, 3H, Ar-CH
3), 4.01 (s.2H, N-CH
2), 6.87 (d,
j=8.1Hz, 1H, Ar-H), 7.06 (d,
j=8.0Hz, 1H, Ar-H), 7.14 (d,
j=8.0Hz, 1H, Ar-H), 7.28 (d,
j=8.0Hz, 1H, Ar-H), 7.34 (d,
j=7.8Hz, 1H, Ar-H), 7.46 (s, 1H, Ar-H), 8.31 (d,
j=16.0Hz, 1H, Rr-CH=), 8.35 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 19.3,21.0,56.6,102.4,118.3,118.7,118.8,125.7,126.5,128.4129.5,129.9,130.3,132.4,133.5,135.2,165.7,140.3,172.2,173.3,190.1.MS (ESI-MS): m/z=386.1 [M+H
+] .Anal.Calcd.ForC
21h
17clFNO
3: C, 65.25; H, 4.31; N, 3.56; Found:C, 65.37; H, 4.44; N, 3.63.
n-(3,4-3,5-dimethylphenyl)-3-[3-(2,4 dichloro benzene base)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i26)
Yellow solid, fusing point higher than 250 DEG C, yield: 62.1%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.25 (s, 3H, Ar-CH
3), 2.29 (s, 3H, Ar-CH
3), 4.18 (s.2H, N-CH
2), 7.16 (d,
j=8.0Hz, 1H, Ar-H), 7.25 (t,
j=8.0Hz, 1H, Ar-H), 7.33 (s, 1H, Ar-H), 7.42 (d,
j=8.0Hz, 1H, Ar-H), 7.45 (d.1H, Ar-H), 7.77 (s, 1H, Ar-H), 7.84 (d,
j=16.0Hz, 1H, Rr-CH=), 8.29 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 19.3,20.2,56.4,102.8,117.2,120.7,121.1,127.3,127.8,129.5,130.2,133.2,133.9,135.3,136.4,137.2,137.7,138.6,172.5,173.4,190.5.MS (ESI-MS): m/z=401.5 [M+H
+] .Anal.Calcd.ForC
21h
17cl
2nO
3: C, 62.59; H, 4.73; N, 3.41; Found:C, 62.70; H, 4.26; N, 3.48.
n-(3,4-3,5-dimethylphenyl)-3-[3-(4-fluorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i27)
Yellow solid, fusing point higher than 250 DEG C, yield: 65.3%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.25 (s, 3H, Ar-CH
3), 2.29 (s, 3H, Ar-CH
3), 4.19 (s.2H, N-CH
2), 7.15 (d,
j=8.0Hz, 1H, Ar-H), 7.28 (m, 4H, Ar-H), 7.45 (d,
j=8.0Hz, 1H, Ar-H), 7.47 (s.1H, Ar-H), 7.96 (d,
j=16.1Hz, 1H, Rr-CH=), 8.31 (d,
j=16.1Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 19.3,20.2,56.4,102.5,117.4,120.3,121.3,127.3,128.3,131.0,131.8,132.7,133.9,135.4,135.9,137.2,137.3,142.1,172.9,173.6,191.0.MS (ESI-MS): m/z=352.2 [M+H
+] .Anal.Calcd.ForC
21h
18fNO
3: C, 70.12; H, 5.56; N, 4.12; Found:C, 71.78; H, 5.16; N, 3.99.
n-(3,4-3,5-dimethylphenyl)-3-[3-(2,6-dichlorophenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i28)
Yellow solid, fusing point higher than 250 DEG C, yield: 73.1%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.25 (s, 3H, Ar-CH
3), 2.29 (s, 3H, Ar-CH
3), 4.18 (s.2H, N-CH
2), 7.16 (d,
j=8.0Hz, 1H, Ar-H), 7.19 (t, 1H, Ar-H), 7.34 (d,
j=8.0Hz, 1H, Ar-H), 7.37 (d,
j=8.0Hz, 2H, Ar-H), 7.45 (s.1H, Ar-H), 8.02 (d,
j=16.0Hz, 1H, Rr-CH=), 8.05 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 19.3,20.2,56.4,103.2,117.3,120.7,121.1,126.5,127.8,129.0,130.2,133.1,133.9,135.5,136.4,137.2,137.7,138.6,172.5,173.2,190.2.MS (ESI-MS): m/z=401.1 [M+H
+] .Anal.Calcd.ForC
21h
17cl
2nO
3: C, 62.11; H, 5.07; N, 4.20; Found:C, 62.70; H, 4.26; N, 3.48.
n-(3,4-3,5-dimethylphenyl)-3-[3-(2-chloro-phenyl-)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i29)
Yellow solid, fusing point higher than 250 DEG C, yield: 55.7%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.25 (s, 3H, Ar-CH
3), 2.29 (s, 3H, Ar-CH
3), 4.19 (s.2H, N-CH
2), 7.16 (d,
j=8.0Hz, 1H, Ar-H), 7.30 (m, 4H, Ar-H), 7.43 (d,
j=8.0Hz, 1H, Ar-H), 7.46 (s.1H, Ar-H), 7.86 (d,
j=16.0Hz, 1H, Rr-CH=), 8.30 (d,
j=16.0Hz, 1H, CO-CH=).
13cNMR (500MHz, CDCl
3, ppm),
δ: 19.3,20.2,56.4,102.7,117.3,120.3,121.1,127.3,128.3,130.0,131.8,132.7,133.9,135.4,135.9,137.2,137.7,140.1,172.7,173.8,190.5.MS (ESI-MS): m/z=348.2 [M+H
+] .Anal.Calcd.ForC
21h
18clNO
3: C, 68.07; H, 5.15; N, 4.04; Found:C, 62.70; H, 4.26; N, 3.48.
n-(3,4-3,5-dimethylphenyl)-3-[3-(2-p-methoxy-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone (compound
i30)
Yellow solid, fusing point higher than 250 DEG C, yield: 55.7%,
1hNMR (500MHz, CDCl
3, ppm),
δ: 2.21 (s, 3H, Ar-CH
3), 2.29 (s, 3H, Ar-CH
3), 3.94 (s.3H, O-CH
3), 4.17 (s.2H, N-CH
2), 6.90 (d,
j=7.5Hz, 1H, Ar-H), 6.93 (d,
j=8.0Hz, 1H, Ar-H), 7.14 (d,
j=8.0Hz, 1H, Ar-H), 7.30 (m, 2H, Ar-H), 7.43 (d,
j=8.0Hz, 1H, Ar-H), 7.46 (s.1H, Ar-H), 7.74 (d,
j=8.0Hz, 1H, Ar-H), 7.95 (d,
j=16.0Hz, 1H, Rr-CH=), 8.27 (d,
j=16.0Hz, 1H, CO-CH=), carbon spectrum does not go out peak .MS (ESI-MS): m/z=386.3 [M+H
+] .Anal.Calcd.ForC
22h
21nO
4: C, 72.72; H, 5.93; N, 4.09; Found:C, 72.71; H, 5.82; N, 3.85.
Embodiment nine, part of compounds are to the inhibit activities testing method of three kind of plant pathogenic fungies
Adopt growth rate method, with fusarium graminearum (
g.zeae), capsicum wilt bacterium (
f.oxysporum), apple decay bacterium (
c.mandshurIca) be tested object, preliminary screening is carried out to the Antifungal Activity in Vitro of target compound.Main employing potato dextrose agar (PDA) substratum, measuring 90mL substratum respectively, to be divided in sterilizing in 200mL triangular flask for subsequent use.The preparation of pastille substratum is all aseptically carried out, and often kind of drug concentration is set to 50 μ g/mL.Take various medicament respectively in 10mL volumetric flask, the aqua sterilisa added containing 0.1%Tween20 is mixed with certain density medicament, add in 90mLPDA substratum (40-50 DEG C), fully shake up, be poured in the culture dish after the sterilizing of diameter 9cm, if three times are repeated, to add the solvent of equivalent for blank.During primary dcreening operation, with fusarium graminearum, capsicum wilt bacterium, apple decay bacterium for screening object, with punch tool (internal diameter 4mm), some bacterium cakes are made in normal for growth bacterium colony punching for subsequent use, with inoculating needle bacterium cake moved and receive dull and stereotyped central authorities, every ware connects a bacterium cake, be placed in 27 DEG C of saturated humidity constant incubators to cultivate, when contrast is covered with, measure colony diameter.Each bacterium colony measures 2 times by right-angled intersection method, represents the size of bacterium colony with its mean number, and the calculation formula of bacteriostasis rate is as follows:
I%＝[(C－T)/(C－0.4)]×100
I is inhibiting rate, and C is blank diameter, and T is process diameter
table 2 n-replace-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds to the inhibition (500 of plant epiphyte
μg/mL)
By
table 2can find out, be 500 in concentration
μduring g/mL, compound
i2,
i3,
i16,
ithe inhibiting rate of 18 pairs of fusarium graminearums is respectively 36.0%, 25.2%, 25.9%, 26.1%, compound
i2,
i3,
i16,
ithe inhibiting rate of 18 pairs of capsicum wilt bacterium is respectively 39.6%, 19.4%, 21.3%, 25.2%.
Embodiment ten, compound are 500
μresisting tobacco mosaic virus live body therapeutic activity test under g/mL concentration.
Select the Nicotiana glutinosa that growing way is consistent, with phosphoric acid buffer, TMV crude extract is diluted to suitable concentration, with the artificial frictional inoculation of writing brush in sprinkled with (full leaf virus inoculation on the of the right age blade of silicon carbide, every blade manually smears virus once gently, left and right half leaf dynamics of smearing is accomplished evenly as far as possible), rinse with clear water after inoculation.After blade is dry, spread compound solution at Zuo Banye, the solvent that right half leaf spreads matched doses compares.In illumination box, moisturizing is cultivated subsequently, and control temperature 23 ± 1 DEG C, illumination 10000Lux, observes after 3 ~ 4d and record the number producing withered spot.Every chemicals treatment establishes 3 strains, every strain 3 ~ 4 leaves.Every medicament carries out 3 repetitions as stated above.
On half leaf of blank, present obvious withered spot, just can investigate after test 3 ~ 4d, record the withered spot number of left and right half leaf of every sheet leaf respectively, be calculated as follows out the inhibiting rate of test compound to plant virus, i.e. relative efficacy.
Representation: Y=(C-A)/C × 100%
Wherein: Y is the inhibiting rate of compound to plant virus.
C is control group (right half leaf) withered spot number, unit: individual.
A is compound treatment group (Zuo Banye) withered spot number, unit: individual.
Wherein control group (right half leaf) withered spot number and compound treatment group (Zuo Banye) withered spot number can join the withered spot sum of mean number or each group repetition repeated with each group.Each process be with oneself second half in contrast, then the process arranging one group of commodity Ningnanmycin is as a comparison.
table 3 n-replace-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds to tobacco mosaic virus (TMV) live body treatment inhibition (500
μg/mL)
From
table 3can find out, when concentration is 500
μduring g/mL, target compound has certain inhibit activities to TMV, compound
i13,
ithe inhibit activities of 15 pairs of tobacco mosaic virus (TMV) live body treatments is respectively 60.2%, 61.2%, higher than contrast medicament Ningnanmycin,
i16,
i22,
ithe inhibit activities of 28 pairs of tobacco mosaic virus (TMV) live body treatments is respectively 55.2%, 49.9%, 47.3%, a little less than the inhibit activities 55.6% of contrast medicament Ningnanmycin.To structure and the biologically active data analysis of compound, find, when the substituting group on phenyl ring is electron-withdrawing group, compound
ithe activity of 15 is the strongest.
Embodiment 11, compound are 250
μresisting tobacco mosaic virus live body therapeutic activity test under g/mL concentration.
table 4 n-replace-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds to tobacco mosaic virus (TMV) live body treatment inhibition (250
μg/mL)
From
table 4can find out, when concentration is 250
μduring g/mL, partial target compound has certain inhibit activities to TMV, compound
i7,
i14,
i15,
i16,
ithe inhibit activities of 28 is respectively 32.3%, 32.1%, 35.7%, 35.9%, 32.1%, a little less than the inhibit activities 45.1% of contrast medicament Ningnanmycin.
Claims (6)
1.
n-replacing-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds, its general structure is as follows:
(
I)
Wherein R
1be 2,3-dichloro, 2-methoxyl group, 2,3-dimethoxys, 2-fluoro-4-bromine, 3-nitro, 4-methyl, 4-bromine, 2-fluorine, 3-bromine, the fluoro-6-chlorine of 2-, 4-fluorine, 3,4-dichloros, 2,6-dichloros, 2-chlorine, 4-chlorine, hydrogen;
R
2for 4-methyl, 3,4-dimethyl.
2. according to claim 1
n-replace-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds, it is characterized in that synthetic compound is as follows:
Each compound structure is as follows:
。
3. as claimed in claim 1 or 2
n-replacement-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds is preparing the application in plant epiphyte resisting and plant virus medicine.
4. according to claim 3
n-replacement-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds compound is preparing the application in plant epiphyte resisting and plant virus medicine, it is characterized in that the medicine for the preparation of resisting tobacco mosaic virus, fusarium graminearum, capsicum wilt bacterium, Valsa mali and medicament.
5. as claimed in claim 1
nthe synthetic method of-replacement-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds, it is characterized in that with substituted aniline, ethyl chloroacetate, methyl aceto acetate, substituted benzaldehyde is raw material, with ethanol, dimethylbenzene, methyl alcohol for solvent be substituted, closed loop, aldol reaction synthesis, its synthetic route is:
R
1be 2,3-dichloro, 2-methoxyl group, 2,3-dimethoxys, 2-fluoro-4-bromine, 3-nitro, 4-methyl, 4-bromine, 2-fluorine, 3-bromine, the fluoro-6-chlorine of 2-, 4-fluorine, 3,4-dichloros, 2,6-dichloros, 2-chlorine, 4-chlorine, hydrogen;
R
2for 4-methyl, 3,4-dimethyl.
6. according to claim 5
nthe synthetic method of-replacement-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds, is characterized in that synthesis step and processing condition are:
The first step:
nthe preparation of-phenylglycine ethyl ester;
Add in there-necked flask substituted aniline, ethyl chloroacetate, 95% ethanol and sodium acetate, wherein mol ratio: substituted aniline: ethyl chloroacetate: sodium ethylate=1:1:1-1:1.2:1, every 5mmol substituted aniline adds the ethanol 10mL of 95%, reflux, TLC follows the tracks of reaction process, adds water after reaction terminates, then extract with benzene, combining extraction liquid, removal of solvent under reduced pressure obtains red-purple solid, obtains white solid with dehydrated alcohol recrystallization
n-phenylglycine ethyl ester;
Second step:
nthe preparation of-replacement-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone;
Get substituted-phenyl glycine ethyl ester, methyl aceto acetate, dry dimethylbenzene joins in there-necked flask, at 125-130 DEG C of backflow 24h, wherein mol ratio: substituted-phenyl glycine ethyl ester: methyl aceto acetate=1:1-1:1.5, every 1.3mmol substituted-phenyl glycine ethyl ester adds the dry dimethylbenzene of 5ml, TLC follows the tracks of reaction process, normal temperature is cooled to after raw material reaction is complete, be Standard entertion concentration by 1.3mmol substituted-phenyl glycine ethyl ester be 1mol/L sodium methylate 15mL, 48h is stirred under normal temperature, TLC follows the tracks of reaction process, after reaction terminates, 20mL water is added in system, pH=2-3 is adjusted to 20% dilute hydrochloric acid, with 20mL dichloromethane extraction 3 times, combining extraction liquid, use saturated common salt water washing, collect organic phase and use anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, removal of solvent under reduced pressure obtains thick product,
Thick product methylene dichloride and recrystallizing methanol obtain solid
n-replace-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone;
3rd step:
nthe preparation of-replacement-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone:
Take
n-replacement-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone, adds anhydrous methanol and 50%KOH joins in there-necked flask, every 2mmol
n-replacement-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone adds anhydrous methanol 20mL, 50%KOH2mL, and stirring at normal temperature 20 minutes, produces a large amount of White Flocculus, add substituted benzaldehyde, wherein mol ratio:
n-replace-3-ethanoyl-4-hydroxypyrrole quinoline-2-ketone: substituted benzaldehyde=1:5; connect prolong backflow 6-8h; TLC follows the tracks of reaction process; after reaction terminates, add 10mL water to system, be adjusted to pH=2-3 with 20% dilute hydrochloric acid; separate out a large amount of yellow solid; natural filtration collects solid, dry for standby, adopts column chromatography for separation to obtain target compound
n-replace-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone.
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| "Synthesis and NMR Spectroscopic Investigations with 3-amino, 3-hydroxy, and 3-methoxy-4-acyl-1-phenyl-2-pyrazolin-5-ones";Wolfgang Holzer等;《HETEROCYCLES》;20040409;第63卷(第6期);1311-1334 * |
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