CN106831587B - Pyrazol acid amide compounds and the preparation method and application thereof - Google Patents
Pyrazol acid amide compounds and the preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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
- C07D231/38—Nitrogen atoms
- C07D231/40—Acylated on said nitrogen atom
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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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
Abstract
The invention discloses a kind of pyrazol acid amide compounds and the preparation method and application thereof.The general structure of the pyrazol acid amide compounds is shown in formula I.There is relevant biological activity 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
Technical field
The invention belongs to plant growth regulator field, it is related to a kind of pyrazol acid amide compounds 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-6) and its conduct ppm
The excellent physiological activity that plant hormone is shown in agricultural crops, synthesis and transformation research are constantly subjected to various countries' science
The favor of family.However high for brassinosteroid synthesis cost and internal metabolism site it is more, easily metabolic inactivation the problem of but
It is helpless, thus the exploration for finding the progress analog exploitation of new target drone receptor increasingly causes people to pay close attention to.
US6667278B2 (2003), which is reported, has copied first kind non-steroidal analog according to the structure and unit of BL, and
Screening obtains high activity BM1 (pM grades), but high concentration (nM or more) shows as no physiological activity, and must assist with (5 μM) of IAA
It is acted on competence exertion.WO2009109570 and US20100152253 is reported when studying glycogen synthase kinase 3 (GSK3s),
It screens to obtain the small molecule Bikinin an of high activity by chemical genetics, it can effectively inhibit BIN2, serve as the competing of ATP
The person of striving, prevents the inactivating phosphorylation of transcription factor, and activity is about the 1/30 of BL.
It is new in order to study discovery in view of the high similarity containing N heteroatomic pyrrazole structure and Bikinin pyridine structure
Type using BIN2 as the regulator of the highly effective and safe of target, present invention design has synthesized in a kind of novel pyrazole amides rape element
Ester analogs.And diversified biological evaluation and preparation application and preparation are carried out to such compound.The change of all designs
Closing object is brand new, is reported for the first time.
Summary of the invention
The object of the present invention is to provide a kind of pyrazol acid amide compounds and the preparation method and application thereof.
Pyrazol acid amide compounds provided by the invention, general structure is shown in formula I,
In the Formulas I, R1=hydrogen or methyl；
R2=methyl or tertbutyloxycarbonyl；
R3=butyric acid base, methyl butyrate base, 2- acetoxy-methyl, 2- methoxy, p-methoxyphenyl, to methoxyl group
Phenethyl or methyl benzoate.
Specifically, compound shown in the Formulas I is any one in following compound:
4- (1H- pyrazoles -3- amino) -4- ketobutyric acid,
4- (1H- pyrazoles -3- amino) -4- oxobutyrate,
4- (1H- pyrazoles -3- amino) -4- oxobutyric,
2- acetoxyl group-N- (1- tertbutyloxycarbonyl-pyrazoles) acetamide,
2- methoxyl group-N- (1- tertbutyloxycarbonyl-pyrazoles) acetamide,
4- methoxyl group-N- (1H- pyrazoles -3- amino) benzoic acid,
4- methoxyl group-N- (1H- pyrazoles -3- amino) phenylacetic acid,
4- methoxycarbonyl group-N- (1H- pyrazoles -3- amino) benzoic acid,
4- methoxyl group-N- [(5- methyl-1 H- pyrazoles) -3- amino] benzoic acid or 4- methoxyl group-N- [(N- methyl-pyrrole
Azoles) -3- amino] benzoic acid.
The method provided by the invention for preparing compound shown in the Formulas I, includes the following steps:
Compound 2 is reacted with concentrated hydrochloric acid, end of reaction obtains compound shown in the Formulas I；
In the compound 2, R1And R3Definition it is identical as in Formulas I.
In the above method, the molar ratio of the compound 2 and concentrated hydrochloric acid is 1:(2-3)；
The reaction carries out in a solvent；The solvent be chosen in particular from tetrahydrofuran, methylene chloride, ethyl acetate, acetone,
At least one of acetonitrile；
The reaction temperature of the reaction is -10-80 DEG C；Reaction time is 2-24h.
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 recrystallization and solvent mashing step, solvent for use is specifically ethyl alcohol；
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 pyrazol acid 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.
Embodiment 1,4- (1H- pyrazoles -3- amino) -4- oxobutyrate (R in formula (I)1And R2It is methyl butyrate for H, R
Base) synthesis
1) synthesis of N-Boc-3- amino-pyrazol
In 100mL round-bottomed flask, 3- amino-pyrazol (10mmol) and di-tert-butyl dicarbonate (Boc) is added2O(14
Mmol), 15mL tetrahydrofuran (solvent A) stirring and dissolving is added DMAP (0.6mmol, 6%) ice salt bath and stirs 2-4 hours, restores
To room temperature, concentration, ethyl acetate/petroleum ether mashing filters to obtain clean product.Solvent mashing method particularly includes: to be purified to 1g
In head product, mixed solvent (V is added dropwiseEthyl acetate/VPetroleum ether=2:1) 5mL, stirring at normal temperature, until product is all precipitated, suction filtration
Obtain clean product.
2) synthesis of 4- [(N-Boc- pyrazoles) -3- amino] -4- oxobutyrate
In 100mL round-bottomed flask bottle, N-Boc-3- amino-pyrazol (10mmol), 3ml (20mmol) triethylamine is added,
15mL tetrahydrofuran stirring and dissolving, ice salt bath are cooled to 0 DEG C, and the 5ml tetrahydro of produced mono-methyl succinyl chloride is added dropwise in constant temperature
Tetrahydrofuran solution, 20min are added dropwise；Ice bath is removed, room temperature is to slowly warm up to, the reaction was continued 2-3 hours, and reaction mixture falls
Enter in 150mL ice water, ethyl acetate extracts (3x100mL), saturated common salt water washing (3x100mL), anhydrous Na2SO4It is dry, mistake
Filter concentration, obtains crude product.
3) synthesis of 4- (1H- pyrazoles -3- amino) -4- oxobutyrate
In 100mL round-bottomed flask, 4- [(N-Boc- pyrazoles) -3- amino] -4- oxobutyrate (10mmol) is added,
It is slowly added dropwise thereto concentrated hydrochloric acid (20mmol-30mmol), reaction mixture, which is stirred at room temperature, to be reacted for 24 hours, and TLC detection is anti-
Answer process.After reaction, it is concentrated, ethyl alcohol mashing purifying.Solvent mashing method particularly includes: into 1g head product to be purified, by
It is added dropwise to ethyl alcohol 5mL, stirring at normal temperature filters to obtain clean product until product is all precipitated.
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 3a-3j is as shown in table 1 below:
Table 1. synthesizes the structure and yield of compound (3a-3j)
The growth regulating-activity measurement of embodiment 2, plant
(1) 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 1/2MS (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.
Test result
All compound test results are as shown in Table 2,3.
2 comparison medicament Hypocotyls Elongation of Arabidopsis measurement result of table
3 Hypocotyls Elongation of Arabidopsis measurement result of table
From above-mentioned 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 at 40 μM
24-epiBL reaches 1.1086 ± 0.0684cm；In the compound of all design synthesis, 3h has Arabidopsis Mutants
Very high elongation activity, maximum value reach 0.8444 ± 0.0416cm；And having 3i, 3j of similar structure with 3h, 3i is but showed by force
The strong activity for inhibiting elongation, minimum value reach 0.1637 ± 0.0230cm, this may be caused due to the nuance of structure.
Embodiment 3, Rice laminae inclination experiment
Rice (OryzasativaLcv.Nipponbare) seed 10%H2O220min is sterilized, sterile water is cleaned, sprouted 3 days in 30 DEG C of incubators, children
Bud illumination cultivation 5-6 days intercepts in the medical fluid that Leaf inclination position is placed in various concentration under 28 DEG C of dark conditions and places 48h, measures
Angle device measures Leaf inclination.
Test result
Test result is as follows for all compounds shown in table 4,5
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 °.All
In the compound for designing synthesis, 3h has very high activity to blade lean, and maximum value reaches 73 ± 6 °；And in hypocotyl
3i, 3j that the effect inhibited is shown as in elongation experiment, although little with 3h architectural difference, that corresponding effect is not presented.
The performance of 3h reactive compound and Hypocotyls Elongation of Arabidopsis experiment are consistent, show that the compound is living with brassinosteroid correlation
Property, while it is low in cost to design compound, under square one, has very high utility value.
Embodiment 4, 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, under subsequent 100% illumination, 65% damp condition, 18h/6h, 26 DEG C/22
DEG C culture 6 days, measure the plant height of wheat, statistic analysis result.
Statistical experiment result is as shown in table 6,7:
Influence of 6 comparison medicament of table to Rice laminae inclination angle
Table 7 synthesizes compound wheat experimental result
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, 3f, 3h, 3i, 3j can control plant height, and wherein minimum value reaches 3.06 ± 0.68cm, similar to Bikinin, simultaneously
The normal growth and development of plant is not contained.In the extreme circumstances, these effects help to prevent the lodging of wheat from occurring, and ensure small
Wheat stable yields and normal economic benefit.
The influence test of embodiment 5, 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 3h, 3i, 3j are demonstrated by higher activity, compares significantly beyond clear water, it is practical and
Bikinin is similar, while promoting the germination under salt stress.In the extreme circumstances, these effects assist in slight salt
Normal growth and the development for coercing lower corn, ensure wheat economic benefit.
Embodiment 6, 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 3f, 3h, 3i, 3j 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.
Experimental result is as shown in table 5:
Inhibiting germination activity of 9 compound of table to weed seed
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 3h, inhibiting rate have reached 33.5% for inhibition；
Followed by 3j has reached 25.3%.In goatweed, best still 3h, inhibiting rate is inhibited to reach 34.8%；Followed by 3j,
Reach 19.3%.3h is also best to the inhibition of wild avena sativa, has reached 27.7%；Followed by 3j reaches
25.5%；3i also has 20.3% inhibiting rate.With the raising of concentration, drug effect may be more preferable, and wherein 3h has very high answer
With value, it is worth subsequent developmental research.
The preparation of embodiment 7, compound 3f water dispersible granules (10%)
3f 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%3f water dispersible granules product.
The water dispersible granules of other general formula compounds can be prepared by the above method.
The preparation of embodiment 8, compound 3h aqueous suspension agent (25%)
Weigh 3h 25g, emulsifier NPEPO44.8g, desugar lignosulfonates 1.2g, together with adding water inventory 70g to add
Enter into sand milling kettle to carry out barreling, after 1h, thickener xanthan gum 0.15g, antifreeze glycol 4g and remaining water are supplied
100%, it in addition system, is modulated, obtains the homogeneous aqueous suspension agent of 3h (25%) white.
The aqueous suspension agent of other general formula compounds can be prepared by the above method.
The preparation of embodiment 9, compound 3i aqueous emulsion (5%)
Weigh 3i 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 10, compound 3j effervescent tablet (1%)
Sealed package after 3j 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 3j 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 11, compound 3a 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 1.0 ml poly alkyl alcohols
Ethylene oxide ether is mixed with 2.0ml 7.5%3a ethanol solution, stirring and emulsifying 10min under 1000rpm.Then, by the emulsion of 3a
1200rpm stirring under be slowly added into the acetum of the chitosan and gelatin that have emulsified, continue stir 45min up to
Mixed liquor is evenly dispersed.Finally by mixed liquor obtained in the spray drying that inlet temperature is 135 DEG C, outlet temperature is 85 DEG C
Curing and drying is carried out in device, gained powder is 3a slow-release microcapsule.After measured, drug encystation rate 83%, carrying drug ratio 3.0%,
20.5 μm of average grain diameter.
The microcapsules of other general formula compounds can be prepared by the above method.
The influence (Hypocotyls Elongation of Arabidopsis experiment) of embodiment 12, different 3h 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 1/2MS (0.8% agar, 1% sucrose and certain density 3h 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 0.02mg/g (20mg/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.
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 3h 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 3h under the concentration of 20mg/L, has highlighted generally effect of the preparation to drug effect is improved, the application study for the later period
Provide certain directive significance.
Attached all characterization of compound data
4- (1H- pyrazoles -3- amino) -4- ketobutyric acid (3a)
1H NMR(300MHz,DMSO-d6) δ 12.16 (s, 2H), 10.36 (s, 1H), 7.56 (d, J=2.3Hz, 1H),
6.45 (d, J=2.3Hz, 1H), 2.62-2.31 (m, 4H)13C NMR(75MHz,DMSO-d6)δ174.05, 169.37,
147.16,129.08,96.03,30.46,29.03.HRMSm/z:184.0717(M+H+,calcd for C7H10N3O3,
184.0717)mp:189.3-191.0℃
4- (1H- pyrazoles -3- amino) -4- oxobutyrate (3b)
1 HNMR(300MHz,DMSO-d6)δ12.26(s,1H),10.41(s,1H),7.57(s,1H),6.46(s,1H),
3.58(s,3H),2.57(s,4H).13C NMR(75MHz,DMSO-d6)δ173.08,169.14,147.15, 129.09,
96.07,51.51,30.32,28.73.HRMS m/z:198.0876(M+H+,calcd for C8H12N3O3, 198.0873)
mp:126.2-127.6℃
4- (1H- pyrazoles -3- amino) -4- oxobutyric (3c)
1H NMR(300MHz,DMSO-d6)δ12.26(s,1H),10.39(s,1H),7.57(s,1H),6.46(s,1H),
4.11-4.00 (m, 2H), 2.55 (s, 4H), 1.17 (t, J=7.1Hz, 3H)13C NMR(75MHz,DMSO-d6)δ172.54,
169.14,147.22,128.97,96.05,60.05,30.33,28.94,14.25.HRMS m/z: 212.1031(M+H+,
calcd for C9H14N3O3,212.1030)mp:148.3-150.3℃
2- acetoxyl group-N- (1- tertbutyloxycarbonyl-pyrazoles) acetamide (3d)
1H NMR(300MHz,DMSO-d6) δ 11.19 (s, 1H), 8.18 (d, J=2.9Hz, 1H), 6.78 (d, J=2.9
Hz,1H),4.64(s,2H),2.10(s,3H),1.56(s,9H).13C NMR(75MHz,DMSO-d6)δ170.12, 166.05,
150.46,147.20,132.06,102.16,84.84,62.26,27.66,20.54.HRMS m/z: 278.1114(M+Na+,
calcd for C11H17N3NaO4,278.1111)mp:118.6-119.9℃
2- methoxyl group-N- (1- tertbutyloxycarbonyl-pyrazoles) acetamide (3e)
1H NMR(300MHz,DMSO-d6) δ 9.11 (s, 1H), 7.98 (d, J=2.9Hz, 1H), 7.00 (d, J=2.9Hz,
1H),4.3(s,2H),3.47(s,3H),1.65(s,9H).13C NMR(75MHz,DMSO-d6)δ168.53, 150.50,
147.20,131.97,102.28,84.77,71.09,58.78,27.64. HRMS m/z:306.1062(M+Na+,calcd
for C12H17N3NaO5,306,1066)mp:77.5-79.6℃
4- methoxyl group-N- (1H- pyrazoles -3- amino) benzoic acid (3f)
1H NMR(300MHz,DMSO-d6)δ12.40(s,1H),10.62(s,1H),8.06–7.95(m,2H),7.63(s,
1H),7.07–6.96(m,2H),6.61(s,1H),3.83(s,3H).13C NMR(75MHz,DMSO-d6)δ 164.21,
162.07,147.14,129.85,129.47,126.54,113.74,97.06,55.54.HRMS m/z: 218.0925(M+H+,calcd for C11H12N3O2,218.0924)mp:194.0-195.0℃
4- methoxyl group-N- (1H- pyrazoles -3- amino) phenylacetic acid (3g)
1H NMR(300MHz,DMSO-d6) δ 12.36 (s, 1H), 10.56 (s, 1H), 7.55 (d, J=2.3Hz, 1H),
7.24 (d, J=8.5Hz, 2H), 6.93-6.82 (m, 2H), 6.43 (d, J=2.2Hz, 1H), 3.72 (s, 3H), 3.52 (s,
2H).13C NMR(75MHz,DMSO-d6)δ168.65,158.10,130.19,128.95,128.23,113.80, 95.86,
55.16,41.71.HRMSm/z:354.1423(M+Na+,calcd for C17H21N3NaO4,354.1424) mp:173.9-
175.5℃
4- methoxycarbonyl group-N- (1H- pyrazoles -3- amino) benzoic acid (3h)
1H NMR(300MHz,DMSO-d6)δ12.59(s,1H),11.02(s,1H),8.16–7.98(m,4H),7.66(d,
J=2.3Hz, 1H), 6.63 (d, J=2.3Hz, 1H), 3.89 (s, 3H)13C NMR(75MHz,DMSO-d6)δ 165.92,
163.91,146.77,132.21,129.51,129.42,129.28,128.33,97.11,52.53.HRMS m/z:
246.0873(M+H+,calcd for C12H12N3O3,246.0873)mp:200.5-202.2℃
4- methoxyl group-N- [(5- methyl-1 H- pyrazoles) -3- amino] benzoic acid (3i)
1H NMR(300MHz,DMSO-d6)δ12.16(s,1H),10.90(s,1H),8.15–7.98(m,4H),6.42(s,
1H),3.89(s,3H),2.23(s,3H).13C NMR(75MHz,DMSO-d6)δ165.81,163.64,147.07, 138.73,
138.49,132.02,129.14,128.20,96.55,52.43,10.91.HRMS m/z: 260.1031(M+H+,calcd
for C13H14N3O3,260.1030)mp:210.7-212.4℃
4- methoxyl group-N- [(N- methyl pyrazole) -3- amino] benzoic acid (3j)
1H NMR(300MHz,CDCl3- d) δ 10.57 (s, 1H), 8.11 (s, 4H), 7.41 (d, J=1.9Hz, 1H),
6.26 (d, J=1.9Hz, 1H), 3.90 (s, 3H), 3.72 (s, 3H) .HRMS m/z:259.2649 (M+H+,calcd for
C13H14N3O3,259.2650)mp:212.0-213.8℃。
Claims (4)
1.3a-3j application of the shown compound in coordinate plant growth activity；
2. the plant growth active regulator containing any compound shown in 3a-3j；
The dosage form of the plant growth active regulator is water dispersible granules, suspending agent, aqueous emulsion, tablet or microcapsules.
Application of any compound in as gramineous weed weedicide in weeding shown in 3.3f, 3h-3j；
The gramineae weed is wild avena sativa, Triticum tauschii, barnyard grass, herba setariae viridis grass or goatweed.
4. the herbicide containing any compound shown in 3f, 3h-3j；
The dosage form of the herbicide is water dispersible granules, suspending agent, aqueous emulsion, tablet or microcapsules.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4772310A (en) * | 1986-06-04 | 1988-09-20 | Bayer Aktiengesellschaft | 5-acylamino-pyrazole derivatives, composition containing them, and their use as herbicides and plant growth |
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| US4772310A (en) * | 1986-06-04 | 1988-09-20 | Bayer Aktiengesellschaft | 5-acylamino-pyrazole derivatives, composition containing them, and their use as herbicides and plant growth |
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| Title |
|---|
| RN 1292998-94-7、1252524-71-2、1249282-22-1、1249087-56-6、1052634-35-1、350255-81-1;ACS;《STN-Registry》;20110511 * |
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