CN110526902A - The synthesis of (N- alkyl indoles)-diketopiperazine compound and purposes as plant growth regulator - Google Patents
The synthesis of (N- alkyl indoles)-diketopiperazine compound and purposes as plant growth regulator Download PDFInfo
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- CN110526902A CN110526902A CN201910896646.5A CN201910896646A CN110526902A CN 110526902 A CN110526902 A CN 110526902A CN 201910896646 A CN201910896646 A CN 201910896646A CN 110526902 A CN110526902 A CN 110526902A
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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
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
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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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The present invention relates to the synthesis of (N- alkyl indoles)-diketopiperazine compound and as the purposes of plant growth regulator, such as logical formula (I) of the chemical structural formula of such compound or (II) are shown:Logical formula (I) and " * " in (II) indicate that chiral centre, spatial configuration are R or S；R1, R2It indicates substituent group, is detailed in specification part.
Description
Technical field
The present invention relates to the synthesis of a kind of (N- alkyl indoles)-diketopiperazine compound and as plant growth regulator
Purposes, belong to pesticide or application field of organic chemistry.
Background technique
Specific gravity of the plant growth regulator in pesticide industry is gradually increased, and has been widely used in modern agricultural production
In: for regulating and controlling the synthesis of plant intracorporal nucleic acid, protein and enzyme；To taking root in plant growth and development process, germinate, carefully
Born of the same parents' elongation, Organ Differentiation, bloom, adjustment effect is played in result, fallen leaves, suspend mode etc..It is had become at present using plant growth regulator
To improve crop yield and improving an important means of quality of agricultural product.Plant modifying agent common at present has indoles second
Acid, indolebutyric acid, gibberellin, ethylene, kinetin, zeatin, methyl α-naphthyl acetate, abscisic acid, phenoxy carboxylic acid derivatives herbicide and benzyl ammonia
Base purine compound etc..Although these plant growth regulator class compounds have played huge effect in agricultural production,
But it is faced with the challenge for not having new construction effective component to release for many years.
Natural products model is not only that the exploitation of novel pesticide provides diversified guide structure, be also used as probe into
The excavation of row pesticide new target drone so promote novel pesticide exploitation (Pest Manag.Sci.2017,73,700-715；
Science 2013,341,742-746).A variety of cookle grade pesticides are developed based on natural products, by taking herbicide as an example,
Such as the natural products glufosinate-ammonium directly used, the sulphur humulone developed based on leptospermone, the cycloheptyl grass developed based on Isosorbide-5-Nitrae-cineole
Ether, endothall based on Cantharidin exploitation etc..How amino acid and derivative peptides or cyclic peptide chemical combination effectively utilized
Object carries out novel pesticide exploitation and has become important direction (Tetrahedron 2010,66,7239-7256.), wherein diketone piperazine
Piperazine class compound (Chem.Rev.2012,112,3641-3716.) is because have extensive bioactivity and chemical catalysis latent
Power causes our concern.Other than the bioactivity such as anticancer, antiviral, anti-oxidant, diketopiperazine compound is also showed
Agricultural antibacterial, desinsection and activity of weeding (J.Agric.Food Chem.2016,64,6659-6671) out, have and carry out novel pesticide
The potentiality of exploitation, if Thaxtomin class natural products shows preferable activity of weeding, by U.S. Marrone Bio
Innovations, INC company apply for the patent disclosure of natural herbicide used in organic paddy rice planting system
(US2010/0267560)。
Indolyl diketopiperazine compounds class natural products from tryptophan shows extensive structure diversity
(J.Agric.Food Chem.2016,64,6659-6671), structural analysis it is found that isopentene group in such natural products and
Similar group is seldom connected on the NH of indole ring.N- alkyl indoles-diketopiperazine is structure novel in such compound
One kind, Japanese Scientists once isolated novel two with significant resisting rice blast bacteria from from the bacterial strain M-3 of ocean
Ketone piperazine compounds: indoles-N- isopentene group-tryptophan-valine diketopiperazine (JP2001247566A,
J.Antibiot.2003,56,102-106.).There has been no the report that such natural products and stereoisomer synthesize, mirror at present
The structural similarity of Yu Qiyu Thaxtomin class natural products, plant growth regulating activity need to be explored.This patent is related to this
The stereoselective syntheses of class natural products, structure optimization, and find that it has the potentiality as plant growth regulator, especially
It is the effect for promoting plant establishment germination.Compared to the Thaxtomin class compound with herbicide effect of patent protection, this is specially
The compound that benefit is related to is readily synthesized, this has positive effect to the initiative of novel pesticide.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of (N- alkyl indoles)-diketopiperazine compound and
Its application as plant growth regulator.
(N- alkyl indoles)-diketopiperazine compound provided by the invention has knot shown in logical formula (I) as follows or (II)
Structure,
Logical formula (I) and " * " in (II) indicate that chiral centre, spatial configuration are R or S；
R1, R2Indicate substituent group:
R1Indicate phenyl that hydrogen, the alkyl containing 1-12 carbon, phenyl, benzenesulfonyl, halogen replace, containing 1-6 carbon alkyl
Substituted phenyl, pyridine, pyrimidine；
R2Indicate the benzene that phenyl, hydroxyl that hydrogen, methyl, ethyl, the alkyl containing 3-12 carbon, phenyl, halogen replace replace
Base, benzyl, the benzyl being optionally substituted by a hydroxyl group on phenyl ring, 3- indoles methylene, the 3- indoles methylene being optionally substituted by a hydroxyl group on phenyl ring；
The invention also includes (N- alkyl indoles)-diketopiperazine compounds as shown in logical formula (I) and (II) in pharmacy
Upper acceptable salt.
Compound of the present invention can carry out chemical completion according to following synthetic route.
Boc-protected tryptophan intermediate 1 according to the present invention, can pass through Boc2O is under alkaline condition to color ammonia
The primary amine of acid carries out selective protection to realize.
The synthesis of intermediate 2: weighing intermediate 1 in a round bottom flask, and dissolved with DMF, is added thereto under ice bath strong
Alkali sodium hydride, and it is slowly added to chlorinated hydrocarbon, carry out hydrocarbyl reaction.
The synthesis of intermediate 3 or 6: equivalent weighs the intermediate 2 and another raw material amino acid methyl ester of above-mentioned preparation, with appropriate
Anhydrous methylene chloride (can also be replaced with dichloroethanes) dissolution, be added 1.1 times amount condensing agents (EDCi or HBTU or
PyBOP), the 4-dimethylaminopyridine (DMAP) of catalytic amount (10mol%) is then added, is stirred to react at room temperature, reaction terminates
Afterwards, saturated ammonium chloride solution quenching reaction, washing, evaporating solvent under reduced pressure, column chromatography for separation obtain intermediate 3 or 6.
The synthesis of intermediate 4 or 7: the Boc protecting group in intermediate 3 or 6 removes under the conditions of trifluoroacetic acid.
The synthesis of object 5 or 8: intermediate 4 or 7 realizes ring doing with the methanol solution of ammonium hydroxide or ammonia in reaction medium
Change.
The synthesis of (N- alkyl indoles)-diketopiperazine compound provided by the present invention is cheap and easy to get with raw material, closes
At the feature that step is few and synthesis post-processing is simple, easily operated.
(N- alkyl indoles)-diketopiperazine compound according to the present invention, preferably following compound:
Wherein R1Including following substituent group:
Wherein R2Including following substituent group:
General preparation can be used to apply (N- alkyl indoles)-diketopiperazine compound of the present invention, it can
Use wettable powder, emulsifiable concentrates, sprayable solution, powder or particle.According to common biology and/or the object of chemistry
Parameter is managed, the compound of logical formula (I) and (II) can be prepared with various ways.Suitable preparation selects example are as follows: wettable powder
Agent (WP), water-soluble powder (SP), water-soluble concentrate, emulsifiable concentrates (EC), for example oil disperses in water and water is in oil
The emulsion (EW) of middle dispersion, suspending agent concentrate (SC), dispersible oil-suspending agent (OD), with oil or water is dilute at sprayable solution
Release the suspension of agent, the solution of miscible oil, powder (DP), capsule suspension liquid (CS) composition, for broadcasting sowing and soil pesticide
Particle, injection particle, coated particle and absorbing particles, dispersible particle (WG), water-soluble particle (SG), ULV in water
(ultra-low volume) formula, micro-capsule and wax work.
It, can be with other pesticide activities when using (N- alkyl indoles)-diketopiperazine compound of the present invention
Substance such as insecticide, acaricide, herbicide and fungicide mixing, can also be with safener, fertilizer and/or plant growth regulating
Agent mixing, hybrid mode can be pre-mixed or it is filling mix.
The plant growth regulating activity of (N- alkyl indoles)-diketopiperazine compound provided by the present invention: including sweet wine
Intestines, the compositae plants such as sunflower, lettuce, crowndaisy chrysanthemum, denticulate ixeris herb, chrysanthemum；The Solanaceaes such as tobacco, potato, tomato, capsicum, fructus lycii are planted
Object；The leguminous plants such as soybean, peanut, semen viciae fabae, pea, red bean, mung bean, cowpea, kidney bean and hyacinth bean；The crosses such as radish, Chinese cabbage
Flower section plant；The cucurbitaceous plants such as pumpkin, wax gourd, watermelon, cucumber, balsam pear, sponge gourd；The plant of theaceae such as tea, oil tea；Cotton,
The malvaceae plants such as piemarker, big safflower, hollyhock；The euphorbia plants such as castor-oil plant, cassava, rubber tree, Chinese tallow tree, tung oil tree, Aleurites montana；Apple
The rosaceous plants such as fruit, Chinese pear-leaved crabapple, Malus spectabilis, pears, peach, Lee, apricot, plum, cherry, loquat, hawthorn, strawberry and raspberry；Mandarin orange, orange, shaddock, lemon
The rutaceaes such as lemon；The gramineae plants such as barnyard grass, wheat, rice, corn, barley, sorghum.
Specific embodiment
By following embodiments and determination of activity experimental result, the present invention can be further illustrated and understood, but be not intended to
Limitation the present invention.
Embodiment one: the synthesis of natural products indoles-N- isopentene group-tryptophan-valine diketopiperazine 5
By taking the synthesis of object 5a as an example,
(1) synthesis of compound 1a:
L-Trp (10g, 49mmol) is weighed in eggplant-shape bottle, the dissolution of 100mL dioxane is added, under condition of ice bath
It is slowly added to NaOH aqueous solution (2M, 40mL), is then slowly added to (Boc) thereto2O (13.9g, 63.7mmol), system is certainly
So it is warmed to room temperature, organic solvent is evaporated off under reduced pressure until the reaction is complete in thin-layer chromatography (TLC) tracking and monitoring reaction process,
Be adjusted to pH 2-3 with dilute hydrochloric acid, be extracted with dichloromethane (50mL × 3), organic phase merge after successively with water (40mL × 2) and
After saturated sodium chloride solution (40mL) washing, anhydrous sodium sulfate is dry, and evaporating solvent under reduced pressure obtains product 1a, yield 90%, directly
For reacting in next step.
(2) synthesis of compound 2a:
Intermediate 1a (6.08g, 20mmol) is weighed in clean and dry Schlenk reaction flask, is added under nitrogen protection
Under condition of ice bath, NaH (0.96g, 40mmol) is added thereto in DMF (20mL) dissolution, after magnetic agitation 15min, thereto plus
Enter 3,3- dimethallyl bromide (4.47g, 3.48mL, 30mmol).Reaction system spontaneous recovery is thin to room temperature under magnetic agitation
Layer chromatography (TLC) tracking and monitoring reaction process, until the reaction is complete.50mL water quenching reaction is added into system, with 30mL stone
After oily ether washing reaction liquid, water phase is adjusted to pH 2-3 with dilute hydrochloric acid, is extracted with dichloromethane (40mL × 3), it is organic to be harmonious
After successively being washed with water (30mL × 2) and saturated sodium chloride solution (30mL) after and, anhydrous sodium sulfate is dry, evaporating solvent under reduced pressure
Product 2a is obtained, yield 83% is directly used in and reacts in next step without column chromatographic purifying.
(3) synthesis of compound 3a:
Intermediate 2a (3.72g, 10mmol) and Valine methyl ester hydrochloride (1.67g, 10mmol) are weighed in eggplant type bottle
In, after anhydrous methylene chloride (50mL) dissolution is added, be added thereto DMAP (0.24g, 2mmol) and HBTU (4.93g,
13mmol), triethylamine (2.78mL, 20mmol) is slowly added dropwise, after being added dropwise, magnetic agitation reaction, spontaneous recovery to room temperature,
Thin-layer chromatography (TLC) tracking and monitoring reaction process, until the reaction is complete.Saturated sodium bicarbonate solution (20mL) is added into system
Quenching reaction, and carry out liquid separation；Inorganic phase is extracted (10mL × 2) with methylene chloride.Organic phase successively uses water after merging
After the washing of (20mL × 2) and saturated sodium chloride solution (15mL), anhydrous sodium sulfate is dry, and evaporating solvent under reduced pressure obtains crude product, column
Chromatography purifies to obtain product 3a, yield 69%.
(4) synthesis of compound 4a:
Intermediate 3a (485mg, 1mmol) is weighed in eggplant-shape bottle, under condition of ice bath, it is molten that 5mL anhydrous methylene chloride is added
Trifluoroacetic acid (1.5mL, 20mmol) is slowly added dropwise in Xie Hou thereto, and after being added dropwise, reaction system is restored to room temperature, thin layer
Chromatography (TLC) tracking and monitoring reaction process, fully reacting after about 2.5 hours, liquid separation after saturated sodium bicarbonate tune pH is neutral, liquid separation
Afterwards, inorganic phase is extracted with dichloromethane (10mL × 3), after organic phase merges, after being washed with saturated sodium chloride solution (10mL), and nothing
Aqueous sodium persulfate is dry, and evaporating solvent under reduced pressure obtains crude product, and rapid column chromatography isolates and purifies to obtain product 4a.
(5) synthesis of compound 5a:
Product 4a (1.925g, 5mmol) is weighed in Schlenk bottles, it is slow with syringe under nitrogen protection condition of ice bath
Be added dropwise ammonium hydroxide 6mL, after being added dropwise, system is restored to continue to react to room temperature, thin-layer chromatography (TLC) tracking and monitoring react into
Journey, fully reacting after about 20 hours, evaporating solvent under reduced pressure obtains product 5a after silica gel column chromatography (eluant, eluent: ethyl acetate), white
Color solid, yield 48%.
According to the method described above and step, by changing the configuration of amino acid, realize compound 5a enantiomter 5d and
The synthesis of diastereoisomer 5b, 5c.
Structural Identification data are as follows:
(3S, 6S) -3-isopropyl-6- ((1- (3-methylbut-2-en-1-yl) -1H-indol-3-yl)
Methyl) piperazine-2,5-dione (5a),
1H NMR (400MHz, CDCl3) δ 0.83 (d, J=6.68Hz, 3H, CHCH3), 1.02 (d, J=7.00Hz, 3H,
CHCH3), 1.77 (s, 3H, CCH3), 1.83 (s, 3H, CCH3), 2.35 (m, 1H), 2.99 (dd, J1=14.60Hz, J2=
10.32Hz, 1H), 3.67 (dd, J1=14.60Hz, J2=3.16Hz, 1H), 3.88 (s, 1H), 4.27 (d, J=9.96Hz,
1H), 4.65 (d, J=6.88Hz, 2H), 5.36 (m, 1H), 6.12 (s, br, NH), 6.56 (s, br, NH), 7.00 (s, 1H),
7.12 (dd, J1=7.52Hz, J2=7.36Hz, 1H, Aromatic H), 7.22 (m, 1H, Aromatic H), 7.33 (d, J=
8.28Hz, 1H, Aromatic H), 7.60 (d, J=7.92Hz, 1H, Aromatic H)
ESI-MS calcd for:C21H28N3O2[M+H]+354.22 found 354.35；Calcd for:
C21H27N3NaO2[M+Na]+376.20 found 376.33；
(3R, 6S) -3-isopropyl-6- ((1- (3-methylbut-2-en-1-yl) -1H-indol-3-yl)
Methyl) piperazine-2,5-dione (5b),
1H NMR (400MHz, CDCl3) δ 0.90 (d, J=6.76Hz, 3H, CHCH3), 0.98 (d, J=7.04Hz, 3H,
CHCH3), 1.77 (d, J=1.36Hz, 3H, CCH3), 1.83 (d, J=1.32Hz, 3H, CCH3), 2.32 (m, 1H), 3.02 (dd,
J1=14.56Hz, J2=9.68Hz, 1H), 3.61 (m, 1H), 3.63 (m, 1H), 4.27 (dd, J1=9.68Hz, J2=
3.44Hz, 1H), 4.67 (d, J=6.60Hz, 2H), 5.35 (m, 1H), 6.14 (s, br, NH), 6.53 (s, br, NH), 7.02
(s, 1H), 7.13 (dd, J1=8.20Hz, J2=7.20Hz, 1H, Aromatic H), 7.24 (m, 1H, Aromatic H), 7.33
(d, J=8.24Hz, 1H, Aromatic H), 7.62 (d, J=7.92Hz, 1H, Aromatic H)
13C NMR (100MHz, CDCl3) δ 16.23,18.11,18.64,25.70,30.17,32.31,44.17,54.34,
60.57,107.68,109.86,118.82,119.54,119.67,122.10,127.05,127.48,136.60,136.62,
167.44,168.59.
ESI-MS calcd for:C21H28N3O2[M+H]+354.22 found 354.35；Calcd for:
C21H27N3NaO2[M+Na]+376.20 found 376.33.
(3S, 6R) -3-isopropyl-6- ((1- (3-methylbut-2-en-1-yl) -1H-indol-3-yl)
Methyl) piperazine-2,5-dione (5c),
1H NMR (400MHz, CDCl3) δ 0.90 (d, J=6.76Hz, 3H, CHCH3), 0.98 (d, J=7.08Hz, 3H,
CHCH3), 1.77 (d, J=1.44Hz, 3H, CCH3), 1.83 (d, J=1.28Hz, 3H, CCH3), 2.32 (m, 1H), 3.01 (dd,
J1=14.60Hz, J2=9.92Hz, 1H), 3.62 (m, 1H), 3.64 (m, 1H), 4.27 (dd, J1=9.84Hz, J2=
3.36Hz, 1H), 4.67 (d, J=6.92Hz, 2H), 5.36 (m, 1H), 5.98 (s, br, NH), 6.18 (s, br, NH), 7.02
(s, 1H), 7.13 (m, 1H, Aromatic H), 7.24 (m, 1H, Aromatic H), 7.33 (d, J=8.24Hz, 1H,
Aromatic H), 7.62 (d, J=7.88Hz, 1H, Aromatic H)
ESI-MS calcd for:C21H28N3O2[M+H]+354.22 found 354.35；Calcd for:
C21H27N3NaO2[M+Na]+376.20 found 376.33.
(3R, 6R) -3-isopropyl-6- ((1- (3-methylbut-2-en-1-yl) -1H-indol-3-yl)
Methyl) piperazine-2,5-dione (5d),
1H NMR (400MHz, CDCl3) δ 0.87 (d, J=6.80Hz, 3H, CHCH3), 1.03 (d, J=7.12Hz, 3H,
CHCH3), 1.77 (d, J=1.36Hz, 3H, CCH3), 1.83 (d, J=1.28Hz, 3H, CCH3), 2.39 (m, 1H), 2.97 (dd,
J1=14.44Hz, J2=10.52Hz, 1H), 3.68 (dd, J1=14.44Hz, J2=3.24Hz, 1H), 3.90 (m, 1H), 4.29
(m, 1H), 4.66 (d, J=6.92Hz, 2H), 5.36 (m, 1H), 5.98 (s, br, NH), 6.27 (s, br, NH), 7.01 (s,
1H), 7.13 (dd, J1=8.80Hz, J2=7.56Hz, 1H, Aromatic H), 7.23 (m, 1H, Aromatic H), 7.33 (d,
J=8.24Hz, 1H, Aromatic H), 7.61 (d, J=7.92Hz, 1H, Aromatic H)
13C NMR (100MHz, CDCl3) δ 16.07,18.11,18.84,25.70,30.82,31.30,44.16,55.09,
60.20,107.95,109.87,118.75,119.58,119.66,122.08,126.74,127.48,136.57,136.61,
166.58,167.93.
ESI-MS calcd for:C21H28N3O2[M+H]+354.22 found 354.21；Calcd for:
C21H27N3NaO2[M+Na+] 376.20, found 376.20.
By similar reaction condition, (N- alkyl the indoles)-diketopiperazine compound being related in this patent is realized
Synthesis.
Embodiment two:
The plant growth regulating activity of (N- alkyl indoles)-diketopiperazine compound measures.
The above-mentioned compound being related to is made into series of concentrations with 5 ‰ DMSO or 10 ‰ DMSO aqueous solutions.24 holes are taken to train
Support plate, each hole middle berth enters double-layer filter paper, the medical fluid that every hole liquid-transfering gun adds 300 μ L to prepare, each concentration in triplicate, to contain
There is 5 ‰ DMSO aqueous solution as control group, the seed of prior vernalization is taken out from biochemical cultivation case, it is thin to be added to 24 holes
In born of the same parents' culture plate, 10, every hole seed covers son, is put into illumination box and cultivates after being sealed with preservative film, sprouts to seed
Afterwards, root long and the bud for measuring seed are long and recorded, and the inhibiting rate to root or bud is calculated with this.
The plant growth regulating activity of representative (N- alkyl indoles)-diketopiperazine compound 5d is as shown in table 1.
Table 1, diketopiperazine compound 5d to barnyard grass and sweet wine intestines growth regulating-activity
(N- alkyl the indoles)-diketopiperazine compound 5d synthesized as can be seen from Table 1 shows barnyard grass and sweet wine intestines
Different plant growth regulating activity: it shows certain inhibiting effect to the root and bud of barnyard grass, is lower than in concentration
In the case where 0.1ppm, apparent inhibiting effect still is shown to the bud of barnyard grass；It shows one to the root and bud of sweet wine intestines
Fixed facilitation, in the case where concentration is lower than 1ppm, still the root to sweet wine intestines and bud show apparent facilitation.
The preparation of (N- alkyl indoles)-diketopiperazine compound according to the present invention and as plant growth regulator
Purposes be described by specific example, those skilled in the art can use for reference the content of present invention, it is appropriate change it is former
The links such as material, process conditions realize that corresponding other purposes, correlation change all without departing from the contents of the present invention, all classes
As replace and change it will become apparent to those skilled in the art that be considered as being included in the scope of the present invention it
It is interior.
Claims (7)
1. can receive on logical formula (I) and (N- alkyl indoles)-diketopiperazine compound shown in (II) and its pesticide as follows
Salt,
Wherein, leading to indicates that chiral centre, spatial configuration are R or S in formula (I) " * "；
Substituent R1It indicates: phenyl that hydrogen, the alkyl containing 1-12 carbon, phenyl, benzenesulfonyl, halogen replace, containing 1-6 carbon hydrocarbon
Phenyl, the pyridine, pyrimidine of base substitution；
Substituent R2Indicate: hydrogen, methyl, ethyl, the alkyl containing 3-12 carbon, phenyl, the phenyl of halogen substitution, hydroxyl replace
Phenyl, benzyl, the benzyl being optionally substituted by a hydroxyl group on phenyl ring, 3- indoles methylene, the 3- indoles methylene being optionally substituted by a hydroxyl group on phenyl ring.
2. claim 1 leads to formula (I) and (II) compound represented, which is characterized in that preferably be selected from following compound:
3. the synthesis of (N- alkyl indoles)-diketopiperazine compound shown in claim 1 and 2, it is characterised in that: with color ammonia
Acid is starting material, is utilized (Boc)2O is to NH2Protection, indole ring NH position hydrocarbylation, resulting intermediate and amino acid methyl ester
Dipeptide compounds are condensed into, Boc protecting group is then removed in acid condition, is reacted with the methanol solution of ammonium hydroxide or ammonia
Medium realizes cyclisation, obtains final goal product.
4. (N- alkyl indoles)-diketopiperazine compound is as plant growth regulator in agricultural shown in claim 1 and 2
On application.
5. the application as required by right 4, which is characterized in that the plant includes sweet wine intestines, sunflower, lettuce, crowndaisy chrysanthemum, gutweed
Dish, chrysanthemum；Tobacco, potato, tomato, capsicum, fructus lycii；Soybean, peanut, semen viciae fabae, pea, red bean, mung bean, cowpea, kidney bean
And hyacinth bean；Radish, Chinese cabbage；Pumpkin, wax gourd, watermelon, cucumber, balsam pear, sponge gourd；Tea, oil tea；Cotton, piemarker, big safflower, hollyhock；
Castor-oil plant, cassava, rubber tree, Chinese tallow tree, tung oil tree, Aleurites montana；Apple, Chinese pear-leaved crabapple, Malus spectabilis, pears, peach, Lee, apricot, plum, cherry, loquat, mountain
Short, bristly hair or beard, strawberry and raspberry；Mandarin orange, orange, shaddock, lemon；Barnyard grass, wheat, rice, corn, barley, sorghum.
6. described (N- alkyl the indoles)-diketopiperazine compound is processed into missible oil, water and milk according to the purposes of right 4 and 5
Agent, microemulsion, wettable powder, water dispersible granules, suspending agent, micro-capsule and wax work.
7. the mixing of (N- alkyl indoles)-diketopiperazine compound and other pesticidal active substances described in claim 1 and 2
It uses, mixed component includes insecticide, acaricide, herbicide and fungicide, can also be with safener, fertilizer and/or plant
Growth regulator mixing, hybrid mode can be pre-mixed or it is filling mix.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103118540A (en) * | 2010-07-15 | 2013-05-22 | 农村振兴厅 | Agricultural chemical containing 2,5-diketopiperazine derivative as active ingredient |
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- 2019-09-19 CN CN201910896646.5A patent/CN110526902A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103118540A (en) * | 2010-07-15 | 2013-05-22 | 农村振兴厅 | Agricultural chemical containing 2,5-diketopiperazine derivative as active ingredient |
Non-Patent Citations (4)
| Title |
|---|
| JAMES, ELLE D.A等: "《Two Distinct Cyclodipeptide Synthases from a Marine Actinomycete Catalyze Biosynthesis of the Same Diketopiperazine Natural Product》", 《ACS SYNTHETIC BIOLOGY》 * |
| JUAN F SANZ-CERVERA等: "《Synthesis and evaluation of microtubule assembly inhibition and cytotoxicity of prenylated derivatives of cyclo-l-Trp-l-Pro》", 《BIOORGANIC & MEDICINAL CHEMISTRY》 * |
| KIMURA, YASUO等: "《Brevicompanine C, cyclo-(D-Ile-L-Trp), and cyclo-(D-Leu-L-Trp), plant growth regulators from Penicillium brevi-compactum》", 《JOURNAL OF NATURAL PRODUCTS》 * |
| MAHMOODI等: "《Two Distinct Cyclodipeptide Synthases from a Marine Actinomycete Catalyze Biosynthesis of the Same Diketopiperazine Natural Product》", 《CHEMBIOCHEM》 * |
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