CN103387516B - Compound with herbicidal activity and preparation method thereof - Google Patents
Compound with herbicidal activity and preparation method thereof Download PDFInfo
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- CN103387516B CN103387516B CN201310332975.XA CN201310332975A CN103387516B CN 103387516 B CN103387516 B CN 103387516B CN 201310332975 A CN201310332975 A CN 201310332975A CN 103387516 B CN103387516 B CN 103387516B
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- guanidine
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- VREKOZOAFFCDMY-UUPZAJKSSA-N CC/C=C\C=C/C(C=C)/C=N/CCOC(c1ccccc1O)=O Chemical compound CC/C=C\C=C/C(C=C)/C=N/CCOC(c1ccccc1O)=O VREKOZOAFFCDMY-UUPZAJKSSA-N 0.000 description 1
- ALUFITGOFDIAAA-CSKARUKUSA-N OCC/N=C/c1ccccc1 Chemical compound OCC/N=C/c1ccccc1 ALUFITGOFDIAAA-CSKARUKUSA-N 0.000 description 1
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Abstract
The present invention discloses a compound with herbicidal activity. The compound has a structure shown in a general formula (Ib); in the general formula, R refers to alkyl, halogen atom, hydroxyl and carboxyl at the site 2 or 3 or 4. The invention also discloses a preparation method of the compound. According to the preparation method, beta-Schiff base ethanol reacts with substituted benzoic acid to obtain the compound. The compound disclosed by the invention has an obvious killing or growth inhibition function on dicotyledonous plants and therefore can be used as an effective component of herbicides.
Description
The application is application number is 201210351954.8, and the applying date is on September 20th, 2012, and denomination of invention is the divisional application of " compound with weeding activity and preparation method thereof " patent application.
Technical field
The invention belongs to pesticide field, relate to a kind of compound with weeding activity and preparation method thereof.
Background technology
Guanidine class, ester compound much all have biological activity, and guanidine compound research is relatively early, also more extensive.1974, United States Patent (USP) (US 3803165 A) reported a kind of carbamate with the band imidazoles (guanidine radicals) of anti-microbial effect, and the guanidine radicals in this compound is an integral part of imidazole ring; In the same year, another part of United States Patent (USP) (US 3819626 A) reports a kind of substituted triazole of weeding activity, and same guanidine radicals is the integral part of triazole ring; 1975, Beaman, Alden G found that again the benzimidazole carbamate of 2-nitro has anti-microbial effect (US 3865823 A), is oxidized to nitro with foregoing patent unlike by imidazoles amino unit, but still can regard as on imidazole ring and there is guanidine radicals.1999 German Patent (DE19981028519) report a kind of 2-amino 1 as weedicide and plant-growth regulator, 3,5-triazole-derivative, guanidine based structures is by triazole ring 1, the amino upper nitrogen-atoms composition of 3-two nitrogen-atoms and 2-, it is so the integral part of aromatic heterocycle that its guanidine radicals is appointed.2008, a patent documentation (WO 2008037463 A2) of World Intellectual Property Organization reported part and can strengthen peptide and polypeptide and nucleic acid drug containing guanidine compound and penetrate biomembranous ability.The domestic research to guanidine compound is the synthesis of alkyl guanidine and biological activity mainly.The basic structure of above-mentioned three major types guanidine compound is as follows:
Wherein A structure is the compound of guanidine radicals on imidazole ring, and B structure is the compound of guanidine radicals in triazole ring, and C-structure is alkyl guanidine compound.
Ester group and aldehyde ketone imino-are also active substructure (Ma Jingzhong, the synthesis of Isosorbide-5-Nitrae-dioxide quinoxaline formaldehyde imine and bacteriostatic activity, applied chemistry in common pesticide molecule.2006,23, (6): 637-640; Xie Qinglan etc., the synthesis of two (trialkylated tin) dicarboxylic esters, structure and the general sieve of pesticide activity, chemical journal, 1999,57,210-218).
Summary of the invention
According to novel pesticide molecular design method, certain bioactive substructure will be had and splice, and likely obtain and there is different bioactive novel substance.Object of the present invention is exactly the compound that design preparation is new under above-mentioned background, and provides its preparation method and the application preparing weedicide.
The present invention is on the basis that above-mentioned guanidine compound is studied, propose to have the substituted aroma formic acid β-guanidine radicals ethyl ester with weeding activity and the substituted aroma formic acid β-Containing Schiff-bases ethyl ester two kinds compound of common structural unit, these two kinds of compounds have respectively general formula (I a) and (I b) shown in structure:
General formula (I a) or (I b) in: R is alkyl, halogen atom, hydroxyl, carboxyl on 2 or 3 or 4.
General formula (preparation of I a) compound is that reaction formula is as follows first by thanomin and sulfuric acid O-methyl-isourea Reactive Synthesis sulfuric acid β-guanidine ethanol:
Formula II compound is led to substituted benzoic acid and thionyl chloride Reactive Synthesis; Reaction formula is as follows:
Again by obtained sulfuric acid β-guanidine ethanol and the reaction of logical formula II compound, obtain general formula (I compound a), reaction formula is as follows:
General formula (I b) preparation of compound be first phenyl aldehyde and thanomin are reacted, obtain β-Schiff's base ethanol, reaction formula is as follows:
Again by β-Schiff's base ethanol and logical formula III compound at dense H
2sO
4be obtained by reacting under catalysis general formula (I compound b), reaction formula is as follows:
Solvent for use is water, tetrahydrofuran (THF), methylene dichloride, trichloromethane, ethyl acetate etc. or without solvent.
The compound of the present invention's synthesis has obvious weeding activity, has remarkable killing effect or growth inhibitory effect to dicotyledons, thus can as the effective constituent of weedicide.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of parabromobenzoic acid-β-guanidine ethyl ester;
Fig. 2 is the infrared spectrogram of p-methylbenzoic acid-β-guanidine ethyl ester;
Fig. 3 is the infrared spectrogram of m-bromobenzoic acid-β-guanidine ethyl ester;
Fig. 4 is the infrared spectrogram of m-methyl benzoic acid-β-guanidine ethyl ester;
Fig. 5 is the infrared spectrogram of Whitfield's ointment-β-guanidine ethyl ester;
Fig. 6 is m-methyl benzoic acid-β-benzaldimine ethyl ester infrared spectrogram;
Fig. 7 is the infrared spectrogram of phthalic acid-mono--β-benzaldimine ethyl ester;
Fig. 8 is the infrared spectrogram of Whitfield's ointment-β-benzaldimine ethyl ester.
Embodiment
The present invention is illustrated below by embodiment.
Embodiment 1: the synthesis of m-bromobenzoic acid-β-guanidine ethyl ester
(1) synthesis of sulfuric acid β-guanidine ethanol
Take 2.46g(0.02mol) sulfuric acid O-methyl-isourea, 1.22g(0.02mol) thanomin is dissolved in the beaker containing 10ml water, oil bath 80 DEG C, induction stirring reaction 6h.Carry out rotary evaporation after cooling, steam aqueous solvent.When steaming until anhydrous, obtain colorless transparent viscous liquid, hold over night, become white solid, smash to pieces powdered, add the washing of 15ml anhydrous methanol, by solid suction filtration, methanol wash 1 ~ 2 time, 65 DEG C of vacuum-drying 4h, weigh 2.65g, productive rate about 90%.
(2) synthesis of m-bromo-benzoyl chloride
Taking 2.01g(0.01mol) m-bromobenzoic acid pours (on spherical condensation tube, end interface connects U-shaped moisture eliminator and has device for absorbing tail gas) in single port flask into, measure about 1.1ml(0.015mol again) thionyl chloride, mixing post-heating is to 65 DEG C ~ 70 DEG C, reaction 4h, now release to without hydrogen chloride gas with the inspection of pH test paper, stop heating.Let cool rear underpressure distillation (80 DEG C ~ 85 DEG C) and remove excessive thionyl chloride.Weighed product 1.91g, productive rate about 87%.
(3) synthesis of target compound m-bromobenzoic acid β-guanidine ethyl ester
Take 1.1g(and be about 0.005mol) m-bromo-benzoyl chloride and 0.92g(be about 0.005mol) sulfuric acid β-guanidine ethanol, add (prolong upper end connects U-shaped moisture eliminator and device for absorbing tail gas) in 100ml single port flask, induction stirring, warming-in-water to 70 DEG C reaction.After 5h, reactant becomes thick, terminates reaction, is cooled to room temperature, and add the washing of 20ml saturated sodium bicarbonate, stir, suction filtration is except water-insoluble, and filtrate rotary distillation (65 DEG C ~ 75 DEG C), obtains pale yellow viscous liquid.In flask, add 15ml methyl alcohol, fully stir and make mixture, obtain the mixture of white opacity, cross the filter residue filtering white, obtain lurid filtrate, underpressure distillation (65 DEG C) except methyl alcohol, obtains pale yellow viscous liquid, crystallisation by cooling, vacuum-drying, weigh 0.95g, productive rate 61%.
Embodiment 2: the synthesis of Whitfield's ointment-β-benzaldimine ethyl ester
(1) synthesis of β-Schiff's base ethanol
Take 10.60g(0.1mol) newly steam phenyl aldehyde, add in the 25mL single necked round bottom flask of band magnetic agitation, oil bath pan, put into stirrer, be fixed on the magnetic stirring apparatus of band oil bath pan, 6.10g(0.1mol is dripped under stirring) thanomin, reaction very exothermic, system becomes yellow rapidly.After system temperature reduces to room temperature, be heated to 85 DEG C, stirring reaction 6h, obtain red, transparent thick liquid.By thick product red liquid oil pump vacuum fractionation, collect 148 ~ 150 DEG C of cuts under 12.4mmHg, obtain pale yellow transparent oily matter benzaldimine ethanol, obtain product 11.5g, productive rate 77%.
(2) synthesis of target product Whitfield's ointment-β-benzaldimine ethyl ester
At band magnetic stirring apparatus, β-Schiff's base ethanol that 2.50g (about 0.017mol) synthesizes is added in the 25mL single necked round bottom flask of oil bath pan, add 3.32g(again and be about 0.017mol) Whitfield's ointment, put into magnetic stir bar, start agitator, progressively be warming up to 70 DEG C, mixture is pale yellow oily liquid body.Drip the dense H of 1mL
2sO
4, 110 DEG C of reaction 4h.After being cooled to room temperature, add 20mL ethyl acetate, stirring and dissolving, liquid proceeds to separating funnel, adds saturated NaHCO
3the aqueous solution regulates PH to 7, leaves standstill, point sub-cloud aqueous phase, then uses the water washing of 20mL saturated common salt, and dividing anhydrates adds anhydrous MgSO mutually afterwards
4drying, steams solvent ethyl acetate, solid ethyl alcohol recrystallization.100 DEG C of oven dryings, obtain product 2.8g, productive rate 62%, and melting range is 140 ~ 142 DEG C.
Synthesized other target compound according to aforesaid method, relevant experimental data is in table 1:
Various substituted-phenyl group and position in the part of compounds molecule of table 1 the present invention synthesis
The infrared spectrogram of above-mentioned eight kinds of compounds is respectively as shown in Fig. 1 ~ 8.
Embodiment 3: weeding activity is tested
The consistent rape that germinates, alfalfa are often organized four bowls.Compare by clear water and solvent emulsion blank, respectively by above-mentioned compound preparation different concns (50 ~ 400mg/L) emulsion of the present invention, for plant plumule process.Arrange 3 Duplicate Samples, chemical applied to plants measures the index of correlation of plant for 10 days afterwards, and calculate the inhibiting rate of plant survival rate, fresh weight, root, stem length, experimental result is as shown in table 2 and table 3.
Table 2 new compound is to the growth inhibitory activity of rape
Continued 2 new compound is to the growth inhibitory activity of rape
Table 3 new compound is to the growth inhibitory activity of alfalfa
Continued 3 new compound is to the growth inhibitory activity of alfalfa
Claims (3)
1. general formula is (I compound b)
General formula (I b) in: R is halogen atom, hydroxyl, carboxyl.
2. claim 1 formula of (preparation method of I b) compound, is characterized in that: comprise the step that β-Schiff's base ethanol and logical formula III compound react,
The structural formula of described β-Schiff's base ethanol is:
In logical formula III: R is halogen atom, hydroxyl, carboxyl.
3. compound according to claim 1 is preparing the application in weedicide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310332975.XA CN103387516B (en) | 2012-09-20 | 2012-09-20 | Compound with herbicidal activity and preparation method thereof |
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| CN201310332975.XA CN103387516B (en) | 2012-09-20 | 2012-09-20 | Compound with herbicidal activity and preparation method thereof |
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| CN201210351954.8A Division CN102863358B (en) | 2012-09-20 | 2012-09-20 | Compound with weeding activity and preparation method thereof |
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| CN103387516A CN103387516A (en) | 2013-11-13 |
| CN103387516B true CN103387516B (en) | 2015-02-04 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008037463A2 (en) * | 2006-09-27 | 2008-04-03 | Paolo Botti | Means and methods of enhancing delivery to biological systems |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008037463A2 (en) * | 2006-09-27 | 2008-04-03 | Paolo Botti | Means and methods of enhancing delivery to biological systems |
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