CN110776410B - Triketone compound containing cinnamoyl, preparation method and application thereof - Google Patents
Triketone compound containing cinnamoyl, preparation method and application thereof Download PDFInfo
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- A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
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Abstract
The invention belongs to the technical field of compound synthesis, and particularly relates to a triketone compound containing cinnamoyl, a preparation method and application thereof. The triketone compound containing cinnamoyl provided by the invention has a structure shown in a formula I, and the structure is shown in a general formula I, and the preparation method mainly comprises the following steps: according to the conventional conditions and operation corresponding to rearrangement, a compound with a structure shown in a formula II is contacted with a catalyst in the presence of alkali and a solvent, wherein R isl、R2Each as defined in the specification. The compound of the invention has excellent control effect on single and dicotyledonous weeds such as piemarker, cockspur grass and the like, is even superior to some commercial herbicides, and has good market development prospect.
Description
Technical Field
The invention belongs to the technical field of compound synthesis, and particularly relates to a triketone compound containing cinnamoyl, a preparation method and application thereof.
Background
P-hydroxyphenylpyruvate dioxygenase (HPPD) is an important target enzyme catalyzing the conversion of p-Hydroxyphenylpyruvate (HPPA) to Homogentisate (HGA) in the tyrosine (Tyr) degradation pathway. This catabolism plays an essential role in the metabolism of all aerobic organisms such as plants, animals and microorganisms. In plants, HGA is an important precursor for the biosynthesis of plastoquinones and tocopherols, a physiological necessity for the normal growth of plants. Albinism, necrosis and death symptoms occur in plants in which the enzyme p-hydroxyphenylpyruvate dioxygenase is inhibited. Therefore, HPPD becomes an important target enzyme for developing novel herbicides, and most HPPD inhibitors have the advantages of low toxicity, low application rate, excellent crop selectivity, broad-spectrum weed control, good environmental compatibility and the like. Has become the most important herbicide variety at present and is the hot spot of research of various large pesticide companies.
Approximately 15 p-hydroxyphenylpyruvate dioxygenase inhibiting herbicides have been developed and commercialized in succession from the first commercialization of the p-hydroxyphenylpyruvate dioxygenase inhibiting herbicide, benconazole, in 1980 to nearly forty years now. At present, the reported structures of herbicides using p-hydroxyphenylpyruvate dioxygenase as an action target enzyme belong to three main classes: triketones, pyrazoles and isoxazoles (diketonitriles). However, during the last decades, this herbicide also developed many resistant weeds, resulting in the herbicide not being effective in weed control. Therefore, the development of novel p-hydroxyphenylpyruvate dioxygenase inhibitor micromolecules is very important, and the method has very important significance for designing, synthesizing and developing novel high-efficiency, broad-spectrum and low-toxicity herbicides.
Some triketones have been reported as herbicides, see CN 104557739 a, CN 105272973 a. However, these herbicides are less safe for crops.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a triketone compound containing cinnamoyl, a preparation method and application thereof, and aims to solve part of problems in the prior art or at least alleviate part of problems in the prior art.
The invention is realized by the following steps that the structural general formula of the triketone compound containing the cinnamoyl group is shown as the following formula I:
wherein R islSelected from H, C1-6Wherein the substitution refers to one or more substituents selected from the group consisting of halogen, Cl-4Alkyl radical, Cl-4Alkoxy radical, Cl-4Haloalkyl, nitro, cyano, Cl-4A haloalkoxy group; r2One selected from hydrogen, halogen, cyano, nitro, sulfonyl, R ', OR', NR 'R', C (O) R ', C (O) OR', C (O) NR 'R'; r 'and R' are each independently H, C1-6Alkyl radical, C1-6Haloalkyl or phenyl.
Further, R2The halogen in (A) is F, Cl or Br.
The preparation method of the triketone compound containing cinnamoyl comprises the following steps: contacting a compound having a structure shown in formula II with a catalyst in the presence of a base and a solvent according to conventional conditions and operations for rearrangement, wherein the compound of formula II has the following structure:
Further, the catalyst is selected from at least one of sodium cyanide, potassium cyanide, acetone cyanohydrin, trimethylsilyl cyanide, 1,2, 4-triazole and benzo 1,2, 4-triazole.
Further, the base is selected from at least one of potassium carbonate, sodium carbonate, absolute carbonate, triethylamine and pyridine.
Further, the solvent is selected from at least one of dichloromethane, chloroform, dichloroethane, acetonitrile, toluene, tetrahydrofuran, and benzene.
Further, the reaction temperature of the contact reaction is 0-100 ℃, and more preferably 20-40 ℃; the reaction time is 0.5 to 24 hours, more preferably 5 to 12 hours.
Further, the molar ratio of the compound having the structure represented by formula II to the catalyst and the base is 1:0.01 to 1:0.5 to 4, more preferably 1:0.05 to 1:1 to 3.
The application of the triketone compound containing cinnamoyl in serving as a p-hydroxyphenylpyruvate dioxygenase inhibitor.
The application of the triketone compound containing cinnamoyl in preventing and controlling weeds or in preparing a herbicide.
Further, the weeds are at least one of monocotyledonous weeds or dicotyledonous weeds.
In summary, the advantages and positive effects of the invention are:
the compound disclosed by the invention still has excellent herbicidal activity under a lower dosage, and particularly has excellent effect on monocotyledonous weeds and/or dicotyledonous weeds.
The compound of the invention has excellent control effect on single and dicotyledonous weeds such as piemarker, cockspur grass and the like, is even superior to some commercial herbicides, and has good market development prospect. The weeds of the present invention are plants that grow in a place that is harmful to human survival and activity, and may be non-cultivated wild plants or plants that are not useful to humans. For example, various wild plants in the field in which the crop is planted may be used.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. The specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.
The invention discloses a triketone compound containing cinnamoyl, a preparation method and application thereof. All compounds of the invention were confirmed by nuclear magnetic resonance and high resolution mass spectrometry, as shown in the following examples.
EXAMPLE 1 preparation of cinnamoyl group-containing triketones
In this example, compound 1 can be reacted with compound 2 to obtain a compound having a structure represented by formula II; compounds of the structure shown in formula II are also directly commercially available. Then under the rearrangement reaction condition, the compound with the structure shown in the formula II is contacted with a catalyst in the presence of alkali and a solvent, and the compound with the structure shown in the formula I is obtained through rearrangement.
Wherein R islSelected from H, C1-6One of alkyl and phenyl of (1); r2One selected from hydrogen, halogen, cyano, nitro, R ', OR', NR 'R', C (O) R ', C (O) OR', C (O) NR 'R'. R 'and R' are each independently H, C1-6Alkyl radical, C1-6Haloalkyl or phenyl.
The conditions of the contact reaction are as follows: the reaction temperature is 0-100 ℃, and more preferably 20-40 ℃; the reaction time is 0.5 to 24 hours, more preferably 5 to 12 hours. In the preparation method described in this example, the molar ratio of the compound having the structure represented by formula II to the catalyst and the base is preferably 1:0.01 to 1:0.5 to 4, and more preferably 1:0.05 to 1:1 to 3. The catalyst is preferably at least one selected from sodium cyanide, potassium cyanide, acetone cyanohydrin, trimethylsilyl cyanide, 1,2, 4-triazole and benzo 1,2, 4-triazole. The base is at least one selected from potassium carbonate, sodium carbonate, absolute carbonate, triethylamine and pyridine. The solvent is at least one selected from dichloromethane, chloroform, dichloroethane, acetonitrile, toluene, tetrahydrofuran and benzene.
Specifically, the preparation process can be as follows: dissolving 1.2eq substituted 2 compound in 40ml chloroform, dropwise adding 1eq compound 1 under magnetic stirring at-5-0 ℃, then dropwise adding 2eq triethylamine by using a constant pressure dropping funnel, controlling the dropwise adding speed to keep the temperature at 4-10 ℃, monitoring reaction by TLC, washing with 10% dilute hydrochloric acid (30mlx3), washing with saturated hydrochloric acid (30mlx3), drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain the compound with the structure shown in formula II. Then the compound with the structure shown in the formula II is dissolved in 20ml of chloroform, 14eq acetonitrile, 2eq triethylamine and 0.4eq acetone cyanohydrin are reacted under oil bath at 23 ℃, TLC monitoring is carried out, the reaction liquid is washed by dilute hydrochloric acid (30mlx3) and saturated saline water (30mlx3), the mixture is dried by anhydrous magnesium sulfate, and the solvent is removed under reduced pressure, thus obtaining the compound with the structure shown in the formula I.
The method provided in this embodiment may further include a step of purifying the obtained product, and there is no particular requirement for the purification method, and various purification methods conventionally used by those skilled in the art may be adopted, for example, extraction with an extraction agent, drying with a drying agent, and removing impurities by column chromatography or the like may be adopted.
EXAMPLE 2 preparation of Compounds of formula I
Dissolving 1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-trifluoromethyl cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) through a constant-pressure dropping funnel, reacting at 0 ℃ for 5 hours under stirring, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring, reacting for 12 hours, washing a mother liquor after the reaction is finished with dilute hydrochloric acid (30mlx3), washing with saturated hydrochloric acid (30mlx3), drying with anhydrous magnesium sulfate, and removing a solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-1).
I-1: a solid; m.p.95.6-96.1 ℃.1H NMR(400MHz,Chloroform-d)18.46(s,1H),8.31(d,J＝15.9Hz,1H),7.90(d,J＝15.9Hz,1H),7.75(d,J＝8.1Hz,2H),7.65(d,J＝8.1Hz,2H),2.72(t,J＝6.4Hz,2H),2.57(t,J＝6.5Hz,2H),2.03(p,J＝6.5Hz,2H).
EXAMPLE 3 preparation of the Compound of formula I
Dissolving 5, 5-dimethyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-trifluoromethyl cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) through a constant-pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction with dilute hydrochloric acid (30mlx3), washing with saturated saline water (30mlx3), drying with anhydrous magnesium sulfate, and removing a solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-2).
I-2: a solid; m.p.99.0-99.7 ℃.1H NMR(400MHz,Chloroform-d)18.46(d,J＝0.8Hz,1H),8.35(d,J＝15.9Hz,1H),7.91(d,J＝15.9Hz,1H),7.75(d,J＝8.2Hz,2H),7.66(d,J＝8.2Hz,2H),2.60(s,2H),2.45(s,2H),1.11(s,6H).
EXAMPLE 4 preparation of the Compound of formula I
Dissolving 5-phenyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-trifluoromethyl cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) through a constant-pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction with dilute hydrochloric acid (30mlx3), washing with saturated saline water (30mlx3), drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-3).
I-3: a solid; m.p.153.8-154.2 ℃.1H NMR(400MHz,Chloroform-d)18.51(s,1H),8.37(d,J＝15.9Hz,1H),7.94(d,J＝15.9Hz,1H),7.76(d,J＝8.1Hz,2H),7.66(d,J＝8.1Hz,2H),7.38(t,J＝7.5Hz,2H),7.32–7.26(m,2H),7.24(s,1H),3.42(tt,J＝10.2,4.9Hz,1H),3.00–2.74(m,4H).
EXAMPLE 5 preparation of the Compound of formula I
Dissolving 5-methyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-trifluoromethyl cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) through a constant pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction with dilute hydrochloric acid (30mlx3), washing with saturated saline water (30mlx3), drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-4).
I-4: a solid; m.p.97.2-98.5 ℃.1H NMR(400MHz,Chloroform-d)18.47(s,1H),8.35(d,J＝15.8Hz,1H),7.92(d,J＝15.9Hz,1H),7.77(d,J＝8.2Hz,2H),7.67(d,J＝8.2Hz,2H),2.82–2.74(m,1H),2.65(ddd,J＝14.3,8.3,2.1Hz,1H),2.48–2.41(m,1H),2.30(ddt,J＝10.0,6.4,2.3Hz,2H),1.14(d,J＝6.0Hz,3H).
EXAMPLE 6 preparation of the Compound of formula I
Dissolving 1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-fluoro cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) by using a constant-pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring, reacting for 12h, washing a mother liquor after the reaction is finished by using dilute hydrochloric acid (30mlx3), washing by using saturated saline acid (30mlx3), drying by using anhydrous magnesium sulfate, and removing a solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-5).
I-5: a solid; m.p.102.8-103.2 ℃.1H NMR(400MHz,Chloroform-d)18.55(s,1H),8.22(d,J＝15.8Hz,1H),7.91(d,J＝15.9Hz,1H),7.72–7.59(m,2H),7.11(t,J＝8.6Hz,2H),2.72(t,J＝6.4Hz,2H),2.62–2.54(m,2H),2.03(p,J＝6.5Hz,2H).
EXAMPLE 7 preparation of the Compound of formula I
Dissolving 5, 5-dimethyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-fluoro cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) by using a constant-pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction with dilute hydrochloric acid (30mlx3), washing with saturated saline water (30mlx3), drying with anhydrous magnesium sulfate, and removing a solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-6).
I-6: a solid; m.p.101.4-102.7 ℃.1H NMR(400MHz,Chloroform-d)18.53(d,J＝0.9Hz,1H),8.25(d,J＝15.8Hz,1H),7.93(d,J＝15.8Hz,1H),7.70–7.65(m,2H),7.15–7.09(m,2H),2.60(s,2H),2.46(s,2H),1.13(s,6H).
EXAMPLE 8 preparation of the Compound of formula I
Dissolving 5-phenyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-fluoro cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) through a constant pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction with dilute hydrochloric acid (30mlx3), washing with saturated saline water (30mlx3), drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-7).
I-7: a solid; m.p.137.8-138.3 ℃.1H NMR(400MHz,Chloroform-d)18.57(d,J＝0.9Hz,1H),8.26(d,J＝15.8Hz,1H),7.94(d,J＝15.8Hz,1H),7.74–7.57(m,2H),7.37(dd,J＝8.1,6.6Hz,2H),7.32–7.27(m,1H),7.24(d,J＝1.9Hz,2H),7.10(t,J＝8.6Hz,2H),3.41(ddt,J＝12.0,10.2,4.9Hz,1H),3.00–2.71(m,4H).
EXAMPLE 9 preparation of the Compound of formula I
Dissolving 5-methyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-fluoro cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) by using a constant-pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction is finished by using dilute hydrochloric acid (30mlx3), washing by using saturated saline solution (30mlx3), drying by using anhydrous magnesium sulfate, and removing a solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-8).
I-8: a solid; m.p.100.5-100.9 ℃.1H NMR(400MHz,Chloroform-d)18.53(d,J＝0.9Hz,1H),8.21(dt,J＝15.9,0.7Hz,1H),7.89(d,J＝15.8Hz,1H),7.68–7.60(m,2H),7.13–7.05(m,2H),2.79–2.70(m,1H),2.62(ddd,J＝11.3,9.4,2.1Hz,1H),2.45–2.36(m,1H),2.26(dddd,J＝11.3,9.9,7.5,3.6Hz,2H),1.11(d,J＝6.0Hz,3H).
EXAMPLE 10 preparation of the Compound of formula I
Dissolving 1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-methyl cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) through a constant-pressure dropping funnel, reacting at 0 ℃ for 5 hours under stirring, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring, reacting for 12 hours, washing a mother liquor after the reaction is finished with dilute hydrochloric acid (30mlx3), washing with saturated saline (30mlx3), drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-9).
I-9: a solid; m.p.106.4-106.8 ℃.1H NMR(400MHz,Chloroform-d)18.56(d,J＝0.9Hz,1H),8.24(dd,J＝15.8,0.9Hz,1H),7.94(d,J＝15.8Hz,1H),7.61–7.49(m,2H),7.21(d,J＝8.0Hz,2H),2.69(t,J＝6.4Hz,2H),2.56(dd,J＝7.1,5.9Hz,2H),2.39(s,3H),2.01(p,J＝6.6Hz,2H).
EXAMPLE 11 preparation of the Compound of formula I
Dissolving 5, 5-dimethyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-methyl cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) by using a constant-pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction with dilute hydrochloric acid (30mlx3), washing with saturated saline water (30mlx3), drying with anhydrous magnesium sulfate, and removing a solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-10).
I-10: a solid; m.p.102.3-102.6 ℃.1H NMR(400MHz,Chloroform-d)18.53(d,J＝0.9Hz,1H),8.27(dd,J＝15.8,0.9Hz,1H),7.95(d,J＝15.8Hz,1H),7.59–7.54(m,2H),7.21(d,J＝7.9Hz,2H),2.57(s,2H),2.41(d,J＝19.5Hz,5H),1.10(s,6H).
EXAMPLE 12 preparation of the Compound of formula I
Dissolving 5-phenyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-methyl cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) through a constant pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction with dilute hydrochloric acid (30mlx3), washing with saturated saline water (30mlx3), drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-11).
I-11: a solid; m.p.145.9-146.2 ℃.1H NMR(400MHz,Chloroform-d)18.58(d,J＝0.9Hz,1H),8.34–8.25(m,1H),7.98(dd,J＝15.8,2.7Hz,1H),7.62–7.53(m,2H),7.40–7.34(m,2H),7.31–7.26(m,2H),7.25–7.20(m,3H),3.46–3.36(m,1H),2.98–2.73(m,4H),2.39(s,3H).
EXAMPLE 13 preparation of the Compound of formula I
Dissolving 5-methyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-methyl cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) by using a constant pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction is finished by using dilute hydrochloric acid (30mlx3), washing by using saturated saline solution (30mlx3), drying by using anhydrous magnesium sulfate, and removing a solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-12).
I-12: a solid; m.p.99.6-100.1 ℃.1H NMR(400MHz,Chloroform-d)18.55(d,J＝0.9Hz,1H),8.26(dd,J＝15.7,0.8Hz,1H),7.94(d,J＝15.8Hz,1H),7.62–7.53(m,2H),7.21(d,J＝8.0Hz,2H),2.74(ddd,J＝17.5,3.8,2.0Hz,1H),2.67–2.57(m,1H),2.45–2.34(m,4H),2.30–2.19(m,2H),1.10(d,J＝5.9Hz,3H).
EXAMPLE 14 preparation of the Compound of formula I
Dissolving 1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-bromocinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) through a constant-pressure dropping funnel, reacting at 0 ℃ for 5 hours under stirring, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃ and stirring to react for 12 hours, washing a mother liquor after the reaction is finished with dilute hydrochloric acid (30mlx3), washing with saturated hydrochloric acid (30mlx3), drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-13).
I-13: a solid; m.p.119.9-120.6 ℃.1H NMR(400MHz,Chloroform-d)18.53–18.47(m,1H),8.25(dd,J＝15.8,0.8Hz,1H),7.85(d,J＝15.8Hz,1H),7.56–7.48(m,4H),2.71(t,J＝6.4Hz,2H),2.59–2.53(m,2H),2.02(p,J＝6.5Hz,2H).
EXAMPLE 15 preparation of the Compound of formula I
Dissolving 5, 5-dimethyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-bromocinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) through a constant pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction with dilute hydrochloric acid (30mlx3), washing with saturated saline water (30mlx3), drying with anhydrous magnesium sulfate, and removing a solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-14).
I-14: a solid; m.p.125.3-125.6 ℃.1H NMR(400MHz,Chloroform-d)18.48(d,J＝0.9Hz,1H),8.28(dd,J＝15.8,0.9Hz,1H),7.86(d,J＝15.8Hz,1H),7.55–7.49(m,4H),2.60–2.57(m,2H),2.44(s,2H),1.10(s,6H).
EXAMPLE 16 preparation of the Compound of formula I
Dissolving 5-phenyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-bromocinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) through a constant pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction with dilute hydrochloric acid (30mlx3), washing with saturated saline water (30mlx3), drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-15).
I-15: a solid; m.p.172.1-173.6 ℃.1H NMR(400MHz,Chloroform-d)18.53(d,J＝0.9Hz,1H),8.31(dd,J＝15.9,0.9Hz,1H),7.89(d,J＝15.8Hz,1H),7.60–7.47(m,4H),7.37(dd,J＝8.1,6.6Hz,2H),7.32–7.27(m,1H),7.26–7.22(m,2H),3.47–3.35(m,1H),3.00–2.71(m,4H).
EXAMPLE 17 preparation of the Compound of formula I
Dissolving 5-methyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 4-bromocinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) through a constant pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction with dilute hydrochloric acid (30mlx3), washing with saturated saline water (30mlx3), drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-16).
I-16: a solid; m.p.121.7-122.2 ℃.1H NMR(400MHz,Chloroform-d)18.49(d,J＝0.9Hz,1H),8.26(dd,J＝15.8,0.9Hz,1H),7.85(d,J＝15.8Hz,1H),7.55–7.48(m,4H),2.75(ddd,J＝17.7,3.8,2.0Hz,1H),2.62(ddd,J＝14.3,8.2,2.1Hz,1H),2.45–2.38(m,1H),2.31–2.20(m,2H),1.11(d,J＝6.0Hz,3H).
EXAMPLE 18 preparation of the Compound of formula I
Dissolving 1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 2-fluoro cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) through a constant-pressure dropping funnel, reacting at 0 ℃ for 5 hours under stirring, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring, reacting for 12 hours, washing a mother liquor after the reaction is finished with dilute hydrochloric acid (30mlx3), washing with saturated saline (30mlx3), drying with anhydrous magnesium sulfate, and removing a solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-17).
I-17: a solid; m.p.92.4-93.1 ℃.1H NMR(400MHz,Chloroform-d)18.72–18.30(m,1H),8.30(d,J＝16.0Hz,1H),8.12(d,J＝16.0Hz,1H),7.74(td,J＝7.6,1.8Hz,1H),7.38(ddd,J＝5.4,4.4,1.8Hz,1H),7.18–7.07(m,2H),2.71(t,J＝6.4Hz,2H),2.57(dd,J＝7.1,5.9Hz,2H),2.02(p,J＝6.6Hz,2H).
EXAMPLE 19 preparation of the Compound of formula I
Dissolving 5, 5-dimethyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 2-fluoro cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) by using a constant-pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction with dilute hydrochloric acid (30mlx3), washing with saturated saline water (30mlx3), drying with anhydrous magnesium sulfate, and removing a solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-18).
I-18: a solid; m.p.101.4-101.8 ℃.1H NMR(400MHz,Chloroform-d)18.48(d,J＝0.9Hz,1H),8.34(dd,J＝16.1,0.9Hz,1H),8.13(d,J＝16.0Hz,1H),7.74(td,J＝7.6,1.8Hz,1H),7.43–7.32(m,1H),7.22–7.05(m,2H),2.59(s,2H),2.44(s,2H),1.11(s,6H).
EXAMPLE 20 preparation of the Compound of formula I
Dissolving 5-phenyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 2-fluoro cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) through a constant pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction with dilute hydrochloric acid (30mlx3), washing with saturated saline water (30mlx3), drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-19).
I-19: a solid; m.p.108.5-109.0 ℃.1H NMR(400MHz,Chloroform-d)18.54(s,1H),8.36(d,J＝16.8Hz,1H),8.16(d,J＝16.0Hz,1H),7.75(td,J＝7.6,1.7Hz,1H),7.43–7.33(m,3H),7.32–7.27(m,1H),7.24(s,2H),7.19(t,J＝7.0Hz,1H),7.11(dd,J＝11.1,7.7Hz,1H),3.41(ddd,J＝15.9,6.5,4.9Hz,1H),3.00–2.71(m,4H).
EXAMPLE 21 preparation of the Compound of formula I
Dissolving 5-methyl-1, 3-cyclohexanedione (10mmol) in 40ml chloroform, dropwise adding 2-fluoro cinnamoyl chloride (10mmol), dropwise adding triethylamine (20mmol) by using a constant-pressure dropping funnel, reacting for 5h under stirring at 0 ℃, then sequentially adding acetonitrile (140mmol), triethylamine (20mmol) and acetone cyanohydrin (4mmol), heating to 23 ℃, stirring and reacting for 12h, washing a mother liquor after the reaction with dilute hydrochloric acid (30mlx3), washing with saturated saline solution (30mlx3), drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain the compound with the structure shown in the formula (I-20).
I-20: a solid; m.p.103.5-103.9 ℃.1H NMR(400MHz,Chloroform-d)18.50(s,1H),8.32(d,J＝15.9Hz,1H),8.12(d,J＝16.0Hz,1H),7.74(t,J＝6.7Hz,1H),7.43–7.32(m,1H),7.22–7.07(m,2H),2.80–2.70(m,1H),2.68–2.57(m,1H),2.47–2.36(m,1H),2.33–2.18(m,2H),1.11(d,J＝6.0Hz,3H).
EXAMPLE 22 study of the inhibitory Activity of cinnamoyl-containing triketones against Hydroxyphenylpyruvate dioxygenase
P-hydroxyphenylpyruvate dioxygenase: the p-hydroxyphenylpyruvate dioxygenase used in the experiment is prepared by expressing and purifying arabidopsis thaliana HPPD. The preparation is carried out according to the method described in the document Agric.food chem.2015,63, 5587-5596.
According to the method described in the literature "Ind. crop.crop.Prod.2019, 137, 566-575", the enzyme activity test is carried out to obtain the cinnamoyl-containing triketone compound of the invention and the contrast requirement on the activity of p-hydroxyphenylpyruvate dioxygenase (the half inhibitory concentration IC of the inhibitor)50) As shown in the following table:
the herbicidal activity test was carried out according to the method described in the chinese patent publication No. CN 104557739 a, and the herbicidal activity inhibition rates (%) of the cinnamoyl group-containing triketone compounds of the present invention and the control requirements for cockspur grass, crab grass, green bristlegrass, piemarker, redroot amaranth, eclipta prostrata were obtained as follows:
the results of the invention show that the compounds I-5, I-13, I-16, I-17, I-18 and I-19 provided by the invention have excellent 4-hydroxyphenylpyruvate dioxygenase inhibition activity and herbicidal activity, and can achieve the effect of the compound with the most excellent effect in the prior art.
In particular, the control effect of the compound I-13 on 4-hydroxyphenylpyruvate dioxygenase is remarkably superior to that of the commercial herbicide mesotrione of 0.275 mu M.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. The preparation method of the triketone compound containing the cinnamoyl group is characterized in that the structural general formula of the triketone compound containing the cinnamoyl group is shown as the following formula I:
wherein R islIs selected from C1-6One of the alkyl groups of (a); r2One selected from hydrogen, halogen and R'; r' is C1-6Alkyl radical, C1-6A haloalkyl group; r2The halogen in (A) is F, Cl or Br;
the preparation method comprises the following steps: contacting a compound having a structure shown in formula II with a catalyst in the presence of a base and a solvent according to the conventional conditions and operation of a rearrangement reaction, wherein the compound of formula II has the following structure:
2. the method for preparing the cinnamoyl group-containing triketone compound according to claim 1, wherein: the catalyst is acetone cyanohydrin.
3. The method for preparing the cinnamoyl group-containing triketone compound according to claim 1, wherein: the alkali is at least one of potassium carbonate, sodium carbonate, triethylamine and pyridine; the solvent is at least one selected from dichloromethane, trichloromethane, dichloroethane, acetonitrile, toluene, tetrahydrofuran and benzene; the reaction temperature of the contact reaction is 0-100 ℃, and the reaction time is 0.5-24 h.
4. The method for preparing the cinnamoyl group-containing triketone compound according to claim 1, wherein: the compound with the structure shown in the formula II is prepared by reacting a compound 1 with a compound 2, wherein the structures of the compound 1 and the compound 2 are as follows:
5. the method for preparing the cinnamoyl group-containing triketone compound according to claim 1, wherein: the molar ratio of the compound with the structure shown in the formula II to the catalyst and the alkali is 1:0.01-1: 0.5-4.
6. Use of the cinnamoyl group-containing triketone compound prepared by the preparation method according to any one of claims 1 to 5 as a p-hydroxyphenylpyruvate dioxygenase inhibitor.
7. Use of the cinnamoyl group-containing triketone compound prepared by the preparation method according to any one of claims 1 to 5 for controlling weeds or for preparing a herbicide.
8. Use of the cinnamoyl group-containing triketone compound according to claim 7 for controlling weeds, wherein: the weeds are at least one of monocotyledonous weeds or dicotyledonous weeds.
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| US4724263A (en) * | 1986-06-09 | 1988-02-09 | Stauffer Chemical Company | Certain 2-phenylacetyl-1,3,5-cyclohexanetriones |
| US4957538A (en) * | 1988-11-18 | 1990-09-18 | Ici Americas Inc. | Certain 2-(2',3',4'-trisubstituted benzoyl)-1,3-cyclohexanediones |
| KR20120123735A (en) * | 2004-06-03 | 2012-11-09 | 이시하라 산교 가부시끼가이샤 | Triketone compounds, method for producing those and herbicide containing those |
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| CN104557739B (en) * | 2013-10-25 | 2016-11-09 | 山东先达农化股份有限公司 | Triketone compound and preparation method and application thereof |
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