CN106810497B - Quinoline amide compound and the preparation method and application thereof - Google Patents

Quinoline amide compound and the preparation method and application thereof Download PDF

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CN106810497B
CN106810497B CN201710047153.5A CN201710047153A CN106810497B CN 106810497 B CN106810497 B CN 106810497B CN 201710047153 A CN201710047153 A CN 201710047153A CN 106810497 B CN106810497 B CN 106810497B
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quinoline
amino
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CN106810497A (en
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段留生
刘少金
于春欣
胡堂路
于莎
周于毅
李召虎
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China Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D215/38—Nitrogen atoms
    • C07D215/40—Nitrogen atoms attached in position 8
    • 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
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings

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  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Agronomy & Crop Science (AREA)
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Abstract

The invention discloses a kind of quinoline amide compounds and the preparation method and application thereof.The general structure of the quinoline amide compound is shown in formula I.There is bioactivity verifying discovery some of them compound special brassinosteroid to react, and as promoted Arabidopsis Mutants det2-1 hypocotyl elongation in dark, rice leaf inclination increases, and enhance the ability etc. of the resistance to salt stress of corn.Individual compound just has very high response in low concentration, in addition in high concentration, moreover it is possible to inhibit the plant height of wheat, retarding of growing improves its ability resistant to lodging.There is on the gramineae weeds such as control of wild oats, Triticum tauschii, barnyard grass, herba setariae viridis grass, goatweed good control efficiency simultaneously.Series compound preparation is easy, low in cost, and agriculture application and popularization value is high, and subsequent further investigation is worth to be developed.

Description

Quinoline amide compound and the preparation method and application thereof
Technical field
The invention belongs to plant growth regulator field, it is related to a kind of quinoline amide compound and preparation method thereof and answers With.
Background technique
Brassinosteroid is also known as brassin lactones (BRs), is a kind of endogenous plant growth regulating by synthesizing in plant Agent.It is adjustable a variety of enzymes required for plant itself and hormone, gives full play to plant itself potential and growth vigor, enhancing life Life vigor and the waterlogging ability of drought resisting.It is extremely low (less than 10 in view of the content in plant such as brassin lactones-6Ppm) and it is as plant The excellent physiological activity that object hormone is shown in agricultural crops, synthesis and transformation research are constantly subjected to scientists from all over the world Favor.However high for brassinosteroid synthesis cost and internal metabolism site it is more, easily metabolic inactivation the problem of but beam Hand is without plan, thus the exploration for finding the progress analog exploitation of new target drone receptor increasingly causes people to pay close attention to.
US6667278 (2003), which is reported, has copied first kind non-steroidal analog according to the structure and unit of BL, and sieves Choosing obtains high activity BM1 (pM grades), but high concentration (nM or more) shows as no physiological activity, and must cooperate with IAA (5 μM) It can play a role.
Summary of the invention
The object of the present invention is to provide a kind of quinoline amide compounds and the preparation method and application thereof.
Quinoline amide compound provided by the invention, general structure is shown in formula I,
In the Formulas I, R be butyric acid base, methyl butyrate base, Boc- glutamic acid base, Boc- asparagine acidic group, to methoxy benzene Base, to anisylethyl or methyl benzoate base.
Specifically, compound shown in the Formulas I is any one in following compound:
4- (quinoline -8- amino) -4- ketobutyric acid,
4- (quinoline -8- amino) -4- oxobutyrate,
4- (quinoline -8- amino) -4- oxobutyric,
N2(tertbutyloxycarbonyl)-N5(quinoline -8- amino) glutamine,
N2(tertbutyloxycarbonyl)-N4(quinoline -8- amino) asparagine,
4- methoxyl group-N- (quinoline -8- amino) benzoic acid,
4- methoxyl group-N- (quinoline -8- amino) phenylacetic acid or 4- methoxycarbonyl group-N- (quinoline -8- amino) benzoic acid.
The method of compound shown in preparation formula I provided by the invention, includes the following steps:
Compound shown in Formula II and reactant III are subjected to acylation reaction, end of reaction obtains chemical combination shown in the Formulas I Object；
In the Formula II, R1Definition it is identical as the definition in previously described formula I；
The reactant III be reactant III1, reactant III2 or
The reactant III1 is
The reactant III2 is
In the above method, the molar ratio of the reactant II and reactant III are 1:(0.9-1.2), concretely 1: 1.1；
The reaction carries out in a solvent；The solvent is chosen in particular from tetrahydrofuran, methylene chloride, ethyl acetate, acetone At least one of with acetonitrile；
When the reactant III is reactant III1, the acylation reaction carries out in -5 DEG C -5 DEG C or room temperature；Reaction Time is 2-12h, concretely 6h；
The reactant III isWhen, the reaction temperature of the acylation reaction is the reflux of solvent for use Temperature；Reaction time is 1-6h, concretely 2-3h；
When the reactant III is reactant III2, the reaction temperature of the acylation reaction is room temperature；Reaction time is 6-24h, concretely 12h.
The method also includes following steps: it is described after completion of the reaction, reaction system is purified；
The method of the purifying is specially recrystallization or solvent mashing；
In the re-crystallization step, solvent for use is specially ethyl alcohol or ethyl acetate；
In the solvent mashing step, solvent for use is specially ethyl alcohol or ethyl acetate and petroleum by volume ratio for 2:1 The mixed liquor of ether composition；
The solvent mashing step specifically includes: mashing solvent for use, stirring to product being added in Xiang Suoshu reaction system It is precipitated, filters；The amount ratio of the reaction system and solvent mashing step solvent for use is specially 1g:5mL.
In addition, aforementioned present invention provide Formulas I described in compound coordinate plant growth activity in application and contain formula I The plant growth active regulator of compound, also belongs to protection scope of the present invention.
Specifically, the coordinate plant growth activity be it is following any one:
1) promote plant growth；
2) promote stem elongation and/or thickening；
3) seed germination rate is improved；
4) yield is improved；
5) improving quality；
6) enhance plant lodging tolerance；
7) enhance the anti-adversity of plant；
The plant growth active regulator is at least one regulator with following function:
1) promote plant growth
2) promote stem elongation and/or thickening；
3) seed germination rate is improved；
4) yield is improved；
5) improving quality；
6) enhance plant lodging tolerance；
7) enhance the anti-adversity of plant；
The anti-adversity of the enhancing plant is specially the resistance to salt stress ability for enhancing plant；
The plant is specially rice, corn or wheat.
In addition, application of the compound described in the Formulas I that aforementioned present invention provides in weeding and the weeding containing type I compound Agent also belongs to protection scope of the present invention.
Specifically, the grass is gramineae weed；Specially wild avena sativa, Triticum tauschii, barnyard grass, herba setariae viridis grass or goatweed； The dosage form of the plant growth active regulator or herbicide is water dispersible granules, suspending agent, aqueous emulsion, tablet or microcapsules. Carrier in above-mentioned dosage form can be various common carriers, as long as guaranteeing to be convenient for after it is prepared with compound shown in formula I It is applied to site to be processed, such as can be plant, seed or soil；Or be conducive to storage, transport or operation.It carries Body can be solid or liquid, or usually gas but the substance of boil down to liquid.
The compound that the present invention designs synthesis is the special quinoline amide brassinosteroid analogs of a class formation, is passed through There is special brassinosteroid to react for relevant biological activity verifying, discovery some of them compound, as promoted to intend south in dark Mustard mutant det2-1 hypocotyl elongation, rice leaf inclination increase, and enhance the ability etc. of the resistance to salt stress of corn.Individual compound Just there is very high response in low concentration, in addition in high concentration, moreover it is possible to inhibit the plant height of wheat, retarding of growing mentions Its high ability resistant to lodging.Have on the gramineae weeds such as control of wild oats, Triticum tauschii, barnyard grass, herba setariae viridis grass, goatweed simultaneously There is good control efficiency.Series compound preparation is easy, low in cost, and agriculture application and popularization value is high, is worth subsequent Further investigation exploitation.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute State method is conventional method unless otherwise instructed.The raw material can obtain unless otherwise instructed from public commercial source.
The preparation of embodiment 1, compound 1a:
In 100mL round-bottomed flask, 8- aminoquinoline (10mmol) and succinic anhydride (12mmol), 15mL tetrahydro furan is added It mutters (solvent A) stirring and dissolving, solid is precipitated in 2 hours progress acylation reactions of temperature rising reflux, end of reaction cooling down, filters Solid, ethyl alcohol recrystallization purifying.Recrystallization method particularly includes: into 1g head product to be recrystallized, ethyl alcohol 3mL is added dropwise, adds Heat reflux continues the 10min that flows back until head product all dissolves, and rear slow cooling is precipitated solid, filters to obtain clean product.
The preparation of embodiment 2, compound 1b:
In 100mL round-bottomed flask bottle, 8- aminoquinoline (10mmol), succinic anhydride (12mmol), 15mL tetrahydro is added Furans stirring and dissolving, back flow reaction 3h carry out acylation reaction, and solid is precipitated in cooling down, and the solid was filtered, ethyl alcohol recrystallization Purify to obtain intermediate product.It takes intermediate product (10mmol), methanol 3ml dissolution, ice salt bath is cooled to 0 DEG C, and constant temperature is added dropwise produced The 5ml tetrahydrofuran solution of thionyl chloride is obtained, 30min is added dropwise；The reaction was continued 5 hours, and reaction mixture pours into 150mL ice In water, ethyl acetate extracts (3x100mL), saturated common salt water washing (3x100mL), anhydrous Na2SO4Concentration is dried, filtered, slightly Product is purified by ethyl alcohol or re-crystallizing in ethyl acetate.Recrystallization method particularly includes: into 1g head product to be recrystallized, dropwise plus Enter ethyl acetate 3mL, be heated to reflux, until head product all dissolves, continue the 10min that flows back, solid is precipitated in rear slow cooling, takes out Filter to obtain clean product.
The preparation of embodiment 3, compound 1d:
Compound 1d is prepared as follows:
In 100mL round-bottomed flask, 8- aminoquinoline (10mmol), 3mL (20mmol) triethylamine, 15ml tetrahydro furan is added It mutters stirring and dissolving, TBTU (3.531g, 11mmol) and Boc- amino acid (10mmol) is separately added.Reaction mixture be stirred at room temperature into Row acylation reaction 12h, TLC detect reaction process.After reaction, it is concentrated and is dissolved with methylene chloride (50mL), 1M NaOH PH to 10 is adjusted, after system layering, phase of fetching water, 1M HCl is acidified to pH=3, and ethyl acetate extracts (3x100mL), saturated salt solution It washs (3x100mL), anhydrous Na2SO4Concentration is dried, filtered, crude product is purified by ethyl alcohol recrystallization.Recrystallize specific method Are as follows: into 1g head product to be recrystallized, ethyl alcohol 3mL is added dropwise, is heated to reflux, until head product all dissolves, continues to flow back 10min, rear slow cooling are precipitated solid, filter to obtain clean product.
According to upper identical method, the compound of remaining the listed ownership Formulas I of table 1 can be prepared.
The structure and yield of compound 1a-1h is as shown in table 1 below:
Table 1. synthesizes compound (1a-1h) structure and yield
Embodiment 4, Arabidopsis Mutants det2-1 hypocotyl elongation activity experiment
70% ethanol disinfection 1min of Arabidopsis Mutants det2-1 seed, while 1% sodium hypochlorite 15min, sterile water It cleans and is seeded in 1/2 MS (0.8% agar, the compound of 1% sucrose and prescribed concentration)；4 DEG C refrigerator vernalization 3 days, then shift To dark condition, 22 DEG C are cultivated 7 days, and after whole strain is taken pictures, ImageJ software measures its hypocotyl length.
The results are shown in Table 2 for all compound tests.
2 comparison medicament Hypocotyls Elongation of Arabidopsis measurement result of table
In table 2, compound 24-epiBL is 24- epi-brassinolide, CAS 78821-43-9；The CAS of Bikinin is 188011-69-0。
3 Hypocotyls Elongation of Arabidopsis measurement result of table
From table 2,3 as can be seen that 24-epiBL has very high activity, in 1 μM of concentration, hypocotyl length reaches 0.9413 ± 0.0748cm, and reported non-steroidal brassinosteroid analogs Bikinin extends activity and is better than 24- at 40 μM EpiBL reaches 1.1086 ± 0.0684cm；In the compound of all design synthesis, 1d, 1e have Arabidopsis Mutants Certain elongation activity, maximum value reach 0.6366 ± 0.0611cm；And 1g inhibits the elongation of hypocotyl, in high concentration When, length reduces to 0.1559 ± 0.0227cm, while will not influence germination percentage.
Embodiment 5, Rice laminae inclination experiment
Rice (OryzasativaLcv.Nipponbare) seed 10%H2O2 sterilizes 20min, and sterile water is cleaned, sprouted 3 days in 30 DEG C of incubators, children Bud illumination cultivation 5-6 days intercepts Leaf inclination position under 28 DEG C of dark conditions and is placed in various concentration when its length to 11 heart of leaf 48h is placed in medical fluid, protractor measures Leaf inclination, and all compound test results are as shown in Table 3, 4.
Influence of 4 comparison medicament of table to Rice laminae inclination angle
Table 5 synthesizes influence of the compound to Rice laminae inclination angle
From above-mentioned table 4,5 as can be seen that 24-epiBL has very high activity, in 10 μM of concentration, blade pitch angle reaches To 125 ± 9 °, and Bikinin is at 100 μM of maximum concentration, active to be not so good as 24-epiBL, can only achieve 75 ± 8 °；It is set all In the compound for counting synthesis, 1g has very high inhibitory activity to blade pitch angle, and minimum value reaches 10 ± 2 °, performance with Hypocotyls Elongation of Arabidopsis experiment is consistent, shows that compound has the effect for inhibiting brassinosteroid related activity, can be used as oil Rape lactone antagonist application, or as lead compound, continual exploitation research.
Embodiment 6, compound control growth test to wheat seedling
10% dioxygen water sterilization 15-20min of wheat seed, sterile water are cleaned and are seeded in 0.8% agar and prescribed concentration Compound), 25 DEG C of incubator dark are germinateed 2 days, and under subsequent 100% illumination, 65% damp condition, 26 DEG C are cultivated 6 days, measurement The plant height of wheat, statistic analysis result.
The results are shown in Table 6 for statistical experiment:
Influence of 6 comparison medicament of table to Plant Height in Wheat
Table 7 synthesizes influence of the compound to Plant Height in Wheat
From the data in table 6,7 it is known that compound prepared by the present invention has very well wheat seedling retarding of growing Effect, 1b, 1c, 1d, 1g can control plant height, and minimum value reaches 3.10 ± 0.44cm, similar to Bikinin, while not hold back The normal growth and development of plant processed.In the extreme circumstances, these effects help to prevent the lodging of wheat from occurring, and ensure that wheat is steady It produces and normal economic benefit.
The influence test of embodiment 7, compound to Maize Seedling Under Salt Stress biomass
Full seed, corn seed (Zheng Dan 958) in the same size, without mildew, no disease and pests harm are chosen, with control 24- EpiBL (1.0mg/L), Bikinin (40mg/L) and medicament to be measured (40mg/L) room temperature are soaked seed for 24 hours, after the completion of seed soaking, with sterilizing Filter paper suck dry moisture is spare.The seed of seed soaking is placed in the germination box for being covered with quartz sand, 150mM is added in every box NaCl solution 10mL, the vernalization at 28 DEG C in incubator, 25, every box, if 3 repetitions, use clear water processing (CK) as compare, Cultivated in illumination box (daytime: 18h, 26 DEG C；100% illumination, night: 6h, 20 DEG C).Replacement treatment fluid daily, germination is extremely At the 8th day, the biomass of 10 plants of seedling of random measurement (weighs seedling fresh weight, is placed in 80 DEG C of baking ovens and dries 48h, weigh dry weight Amount).
Experimental result is as shown in chart 8:
The influence of 8 comparison medicament of table and compound to corn seedling biomass
From the data in table 8 it is known that certain compounds prepared by the present invention are to the biology under corn seedling salt stress Amount accumulation has the effect of certain, and wherein 1b, 1c, 1g are demonstrated by certain activity, is more than clear water control, reality and Bikinin It is similar, while promoting the germination under stress.In the extreme circumstances, these effects assist in slight maize under NaCl stress Normal growth and development, ensure wheat economic benefit.
Embodiment 8, compound test weed seed Inhibiting germination
Culture dish seed soaking is carried out for 24 hours to weed seed with the medical fluid of the 80mg/L of 1b, 1c, 1d, 1g configuration, sterile water is cleaned It is seeded in bottom to be lined in the 6cm batch cultur ware of two layers of filter paper, it is uniform that every ware uniformly places the big full and size of appropriate grain 20, seed, dark culturing in incubator (daytime: 18h, 25 DEG C；Night: 6h, 20 DEG C), count 3 days germinating energies and 7 days send out Bud rate handles data, analyzes result.
Inhibiting germination activity of 9 compound of table to weed seed
Experimental result is as shown in table 9:
From the results shown in Table 9, under the high drug concentration of 80mg/L, herba setariae viridis grass, goatweed and wild avena sativa Germination is all by a degree of inhibition.In herba setariae viridis grass, most preferably 1g, inhibiting rate have reached 43.7% for inhibition； Followed by 1c has reached 22.2%.In goatweed, best still 1g, inhibiting rate is inhibited to reach 47.5%；Followed by 1c, Reach 21.1%.1g is also best to the inhibition of wild avena sativa, has reached 33.2%；Followed by 1b reaches 17.7%；1c also has 12.7% inhibiting rate.With the raising of concentration, drug effect may be more preferable, and wherein 1g has very high answer With value, it is worth subsequent developmental research.
The preparation of embodiment 9, compound 1b water dispersible granules (10%)
1b 10g, wetting dispersing agent fatty alcohol sulfate salt 6g, disintegrating agent ammonium sulfate 3g, carrier kaolin is weighed to complement to 100g, is sufficiently mixed uniformly, is ground into wettable powder through airslide disintegrating mill, is added in fluidized bed drying pelletizer, with containing The aqueous solution of adhesive polyethylene glycol 2g, it is dry in the fluidized bed prilling of (50 DEG C -70 DEG C), drying machine, it is obtained after screening 10%1b water dispersible granules product.
The water dispersible granules of other general formula compounds can be prepared by the above method.
The preparation of embodiment 10, compound 1c aqueous suspension agent (25%)
Weigh 1c 25g, emulsifier NPEPO44.8g, desugar lignosulfonates 1.2g, together with add water inventory 70g be added It carries out barreling into sand milling kettle, after 1h, thickener xanthan gum 0.15g, antifreeze glycol 4g and remaining water is supplied 100%, It in addition system, is modulated, obtains the homogeneous aqueous suspension agent of 1c (25%) white.
The aqueous suspension agent of other general formula compounds can be prepared by the above method.
The preparation of embodiment 11, compound 1d aqueous emulsion (5%)
Weigh 1d 5g and emulsifier agriculture breast 501#2.8g, co-emulsifier agriculture breast 601#7.2g is added together, and makes to be dissolved into Even oil phase.Water, antifreeze ethylene glycol 5g are mixed, uniform water phase is become.Under room temperature and high-shear emulsion machine stirring, Oily phase is added in water phase, forms well dispersed aqueous emulsion.
The aqueous emulsion of other general formula compounds can be prepared by the above method.
The preparation of embodiment 12, compound 1g effervescent tablet (1%)
Sealed package after 1g 1g is dried 24 hours at 80 DEG C is weighed, oxalic acid 30g, sodium bicarbonate 30g mechanical crushing are arrived 100 mesh, diatomite 0.1g, lactose 3g, white carbon black 31g and talcum powder 5g are mixed evenly, and are crushed to 800 mesh, with 1g mixed Close stirring in blender and be pressed into effervescent tablet after ten minutes, sealed package product.
The tablet of other general formula compounds can be prepared by the above method.
The preparation of 20 μm of embodiment 13, compound 1h partial size microcapsules (3%)
It weighs 2.0g chitosan and 1.0g gelatin is dissolved in the acetum of 100ml 2%, by 2ml Sorbitan acid potassium list Laurate is slowly added into above-mentioned solution under 800rpm stirring, persistently stirs 20min.Again by 1.0ml fatty alcohol polyoxy Vinethene is mixed with 2.0ml 7.5%1h ethanol solution, stirring and emulsifying 10min under 1000rpm.Then, the emulsion of 1h is existed It is slowly added into the acetum of the chitosan and gelatin that have emulsified under 1200rpm stirring, continues to stir 45min until mixed It is evenly dispersed to close liquid.Finally by mixed liquor obtained in the spray dryer that inlet temperature is 135 DEG C, outlet temperature is 85 DEG C Curing and drying is carried out, gained powder is 1h slow-release microcapsule.After measured, drug encystation rate 83%, carrying drug ratio 3.0% are average 20.5 μm of partial size.
The microcapsules of other general formula compounds can be prepared by the above method.
The influence (Hypocotyls Elongation of Arabidopsis experiment) of embodiment 14, different 1g compound formulations to drug effect
70% ethanol disinfection 1min of Arabidopsis Mutants det2-1 seed, while 1% sodium hypochlorite 15min, sterile water It cleans and is seeded in 1/2 MS (0.8% agar, 1% sucrose and certain density 1g compound formulation)；4 DEG C refrigerator vernalization 3 days, with After be transferred under dark condition, 22 DEG C cultivate 7 days, after whole strain is taken pictures, ImageJ software measures its hypocotyl length.Formulation concentrations For 0.025mg/g (25mg/L), preparation method is to add water or DMSO to be diluted to institute by the concentration indicated in the preparation of various concentration The concentration needed.
Test result
All compound test results are as shown in table 10.
10 Hypocotyls Elongation of Arabidopsis measurement result of table
From the data in table 10 it is known that 1g compound formulation prepared by the present invention to the drug effect of arabidopsis hypocotyl all It is better than the processing of pure medicament.Wherein water dispersible granules, aqueous suspension agent, aqueous emulsion and microcapsules are demonstrated by higher activity, It is better than tablet and 1g under the concentration of 25mg/L, has highlighted effect of the preparation to drug effect is improved.The application study in later period is provided Certain directive significance.
Attached all characterization of compound spectrum datas
4- (quinoline -8- amino) -4- ketobutyric acid (1a)
1H NMR(300MHz,DMSO-d6) δ 12.17 (s, 1H), 10.14 (s, 1H), 8.94 (dd, J=4.2,1.7Hz, 1H), 8.61 (dd, J=7.6,1.5Hz, 1H), 8.40 (dd, J=8.3,1.7Hz, 1H), 7.71-7.51 (m, 3H), 2.83 (dd, J=7.5,5.8Hz, 2H), 2.59 (dd, J=7.3,5.9Hz, 2H)13C NMR(75MHz,DMSO-d6)δ174.00, 173.77,148.96,138.20,136.72,134.78,128.02,127.14,122.25,121.87,116.69,31.81, 29.17.HRMS m/z:245.0919(M+H+,calcd for C13H13N2O3,245.0921)mp:140.0-141.7℃
4- (quinoline -8- amino) -4- oxobutyrate (1b)
1H NMR(300MHz,DMSO-d6) δ 10.18 (s, 1H), 8.94 (dd, J=4.2,1.7Hz, 1H), 8.59 (dd, J =7.6,1.4Hz, 1H), 8.41 (dd, J=8.3,1.7Hz, 1H), 7.71-7.51 (m, 3H), 3.61 (s, 3H), 2.89 (dd, J =7.5,5.6Hz, 2H), 2.66 (dd, J=7.5,5.6Hz, 2H)13C NMR(75MHz,DMSO-d6)δ172.95,170.51, 148.85,138.17,136.62,134.67,127.95,127.03,122.14,121.84,116.72,51.50,31.55, 28.79.
HRMS m/z:259.1080(M+H+,calcd for C14H15N2O3,259.1077)mp:88.3-90.4℃
4- (quinoline -8- amino) -4- oxobutyric (1c)
1H NMR(300MHz,DMSO-d6) δ 10.17 (s, 1H), 8.94 (dd, J=4.2,1.7Hz, 1H), 8.60 (dd, J =7.6,1.4Hz, 1H), 8.40 (dd, J=8.3,1.7Hz, 1H), 7.71-7.50 (m, 3H), 4.13-4.00 (m, 2H), 2.88 (dd, J=7.5,5.6Hz, 2H), 2.64 (dd, J=7.5,5.7Hz, 2H), 1.17 (t, J=7.1Hz, 3H)13C NMR (75MHz,DMSO-d6)δ172.41,170.51,148.81,138.16,136.59,134.68,127.93,127.01, 122.11,121.79,116.67,60.04,31.59,29.03,14.16.HRMS m/z:273.1236 (M+H+,calcd for C15H17N2O3,273.1234)mp:90.6-91.8℃
N2(tertbutyloxycarbonyl)-N5(quinoline -8- amino) glutamine (1d)
1H NMR(300MHz,DMSO-d6) δ 12.15 (s, 1H), 10.50 (s, 1H), 8.89 (dd, J=4.2,1.7Hz, 1H), 8.66 (dd, J=7.6,1.4Hz, 1H), 8.43 (dd, J=8.3,1.7Hz, 1H), 7.77-7.54 (m, 4H), 4.24- 4.10 (m, 1H), 2.38 (t, J=7.5Hz, 2H), 2.13 (s, 1H), 1.85 (ddt, J=14.1,9.8,7.4Hz, 1H), 1.44 (s,9H).13C NMR(75MHz,DMSO-d6)δ174.03,171.07,155.91,148.97,138.08,136.77, 134.06,127.93,127.16,122.38,122.08,115.97,78.95,55.28,30.52,28.32,26.39.HRMS m/z:374.1709(M+H+,calcd for C19H24N3O5,374.1710)mp:216.5-218.2℃
N2(tertbutyloxycarbonyl)-N4(quinoline -8- amino) asparagine (1e)
1H NMR(300MHz,DMSO-d6) δ 12.68 (s, 1H), 10.18 (s, 1H), 8.94 (dd, J=4.2,1.7Hz, 1H), 8.65 (dd, J=7.6,1.4Hz, 1H), 8.42 (dd, J=8.3,1.7Hz, 1H), 7.74-7.59 (m, 3H), 7.16 (d, J=8.3Hz, 1H), 4.48-4.34 (m, 1H), 3.03-2.91 (m, 2H), 1.35 (s, 9H)13C NMR(75MHz,DMSO-d6) δ173.38,168.85,155.51,148.95,138.18,136.71,134.60,127.98,127.09,122.26, 122.13,116.78,78.41,50.85,39.00,28.29.HRMS m/z:360.1553(M+H+,calcd for C18H22N3O5,360.1554)mp:167.1-169.0℃
4- methoxyl group-N- (quinoline -8- amino) benzoic acid (3f)
1H NMR(300MHz,DMSO-d6) δ 10.72 (s, 1H), 8.97 (dd, J=4.2,1.7Hz, 1H), 8.71 (dd, J =7.6,1.4Hz, 1H), 8.46 (dd, J=8.3,1.7Hz, 1H), 8.16 (s, 4H), 7.77 (dd, J=8.3,1.4Hz, 1H), 7.73–7.60(m,2H),3.90(s,3H).13C NMR(75MHz,DMSO-d6)δ164.03,162.37,149.11,138.29, 136.80,134.30,129.01,127.91,127.12,126.70,122.34,122.00,116.29,114.33, 55.58.HRMSm/z:279.1132(M+H+,calcd for C17H15N2O2,279.1128)mp:119.1-119.8℃
4- methoxyl group-N- (quinoline -8- amino) phenylacetic acid (3g)
1H NMR(300MHz,DMSO-d6) δ 10.18 (s, 1H), 8.89 (dd, J=4.2,1.7Hz, 1H), 8.61 (dd, J =7.6,1.4Hz, 1H), 8.39 (dd, J=8.3,1.7Hz, 1H), 7.70-7.50 (m, 3H), 7.40-7.28 (m, 2H), 6.98–6.87(m,2H),3.87(s,2H),3.74(s,3H).
13C NMR(75MHz,DMSO-d6)δ170.09,158.35,148.88,136.61,134.64,130.57, 127.90,127.71,127.02,122.13,121.93,116.48,114.06,55.14,43.02.HRMS m/z: 293.1282(M+H+,calcd for C18H17N2O2,293.1285)mp:72.7-73.5℃
4- methoxycarbonyl group-N- (quinoline -8- amino) benzoic acid (3h)
1H NMR(300MHz,DMSO-d6) δ 10.73 (s, 1H), 8.98 (dd, J=4.2,1.7Hz, 1H), 8.72 (dd, J =7.6,1.4Hz, 1H), 8.47 (dd, J=8.3,1.7Hz, 1H), 8.17 (s, 4H), 7.78 (dd, J=8.3,1.4Hz, 1H), 7.74–7.61(m,2H),3.92(s,3H).13C NMR(75MHz,DMSO-d6)δ165.72,163.77,149.33,138.50, 136.88,133.97,132.62,129.85,128.00,127.59,127.12,122.81,122.49,117.06, 52.61.HRMS m/z:307.1081(M+H+,calcd for C18H15N2O3,307.1077)mp:133.7-134.9℃。

Claims (3)

1. application of the compound of formula I in coordinate plant growth activity；
The compound of formula I is any one in following compound:
4- (quinoline -8- amino) -4- ketobutyric acid,
4- (quinoline -8- amino) -4- oxobutyrate,
4- (quinoline -8- amino) -4- oxobutyric,
N2(tertbutyloxycarbonyl)-N5(quinoline -8- amino) glutamine,
N2(tertbutyloxycarbonyl)-N4(quinoline -8- amino) asparagine,
4- methoxyl group-N-(quinoline -8- amino) benzoic acid,
4- methoxyl group-N-(quinoline -8- amino) phenylacetic acid and 4- methoxycarbonyl group-N-(quinoline -8- amino) benzoic acid.
2. application according to claim 1, it is characterised in that: the plant is rice, corn or wheat.
3. application of the compound of formula I in weeding；
The compound of formula I is any one in following compound:
4- (quinoline -8- amino) -4- oxobutyrate,
4- (quinoline -8- amino) -4- oxobutyric,
N2(tertbutyloxycarbonyl)-N5(quinoline -8- amino) glutamine,
N2(tertbutyloxycarbonyl)-N4(quinoline -8- amino) asparagine,
4- methoxyl group-N-(quinoline -8- amino) benzoic acid and 4- methoxyl group-N-(quinoline -8- amino) phenylacetic acid；
The grass is wild avena sativa, Triticum tauschii, barnyard grass, herba setariae viridis grass or goatweed.
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