CN109180667B - 8- (benzofuran-5-yl) benzoxazinone derivative and application thereof - Google Patents
8- (benzofuran-5-yl) benzoxazinone derivative and application thereof Download PDFInfo
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- CN109180667B CN109180667B CN201811048178.8A CN201811048178A CN109180667B CN 109180667 B CN109180667 B CN 109180667B CN 201811048178 A CN201811048178 A CN 201811048178A CN 109180667 B CN109180667 B CN 109180667B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
Abstract
The invention relates to 8- (benzofuran-5-yl) benzoxazinone derivatives shown as formula I and application thereof in preparing pesticides:
wherein R is selected from: hydrogen, C1～C2Alkyl radical, C3～C4Straight-chain or branched alkyl radicals, R1Selected from: c1～C3A linear alkyl group.
Description
Technical Field
The invention relates to the preparation and application of a new compound; in particular to 8- (benzofuran-5-yl) benzoxazinone derivatives and their application as pesticides.
Background
In 2005, Charles et al [ WO 2005099688] described the synthesis of 8- (2, 4-dimethylphenyl) -2-methyl-2H-benzo [ b ] [1,4] oxazin-3 (4H) -one starting from 2-nitro-6-bromophenol:
in 2007, Kuo et al [ US 20070265252] described the synthesis of 8- (3- (trifluoromethyl) phenyl) -2H-benzo [ b ] [1,4] oxazin-3 (4H) -one from 6-bromo-2-aminophenol. The biphenyl oxazinone derivatives are useful as Cholesteryl Ester Transfer Protein (CETP) inhibitors. The preparation process comprises the following steps:
in 2010, Russo et al [ WO 2010111626] described the synthesis of biphenyl oxazinones from 6-bromo-2-methyl-2H-benzo [ b ] [1,4] oxazin-3 (4H) -one as a starting material, which inhibit PARP, delay intracellular DNA repair and enhance cancer therapy. The preparation process comprises the following steps:
in 2016 John et al [ WO 2016038582 ]]Biphenyloxazinones prepared from 2-amino-6-bromo-4-chlorophenol are described, which find utility as Raf kinase inhibitors and in the treatment of certain conditions associated with excess Raf kinase activityThese diseases include diseases such as cancer caused by cell proliferation. IC of excellent compound to C-Raf50The value is 0.02 mug/L, and the strong inhibitory activity is shown. The preparation process comprises the following steps:
disclosure of Invention
The invention aims to provide 8- (benzofuran-5-yl) benzoxazinone derivatives, and a preparation method and application thereof.
In order to solve the technical problem, the invention provides the following technical scheme:
the first aspect of the technical scheme of the invention is an 8- (benzofuran-5-yl) benzoxazinone derivative shown in a chemical structural formula I:
wherein R is selected from: hydrogen, C1～C2Alkyl radical, C3～C4Straight-chain or branched alkyl radicals, R1Selected from: c1～C3A linear alkyl group.
Further, preferred compounds are selected from: 6-allyl-8- (2-methylbenzofuran-5-yl) -2H-benzo [ b ] [1,4] oxazin-3 (4H) -one.
The second aspect of the present invention provides a method for preparing the 8- (benzofuran-5-yl) benzoxazinone derivative according to the first aspect, characterized in that it is prepared by the following reaction:
wherein R is selected from: hydrogen, C1～C2Alkyl radical, C3～C4Straight-chain or branched alkyl radicals, R1Selected from: c1～C3A linear alkyl group.
In a third aspect of the present invention, there is provided the 8- (benzofuran-5-yl) benzoxazinone derivative according to the first aspect of the present invention and its use in the preparation of a pesticide.
According to a third aspect of the present invention there is provided the use of 2-benzylimino-6- (benzofuran-5-yl) phenol as described in the first aspect of the present invention in the preparation of a pesticide.
In a fourth aspect of the present invention, there is provided 4-allyl-2-nitroso-6- (benzofuran-5-yl) phenol represented by the following chemical formula II:
the fifth aspect of the present invention provides a process for producing 4-allyl-2-nitroso-6- (benzofuran-5-yl) phenol according to the fourth aspect, characterized by the following reaction:
wherein the nitrosation agent selected in the nitrosation reaction is nitrous acid or sodium nitrite and concentrated hydrochloric acid, and the concentration of the concentrated hydrochloric acid is 36-38%; the feeding ratio of the 4-allyl-2- (2-methylbenzofuran-5-yl) phenol to the sodium nitrite is 1.0: 1.1-1.5, carrying out nitrosation reaction in acetonitrile and water.
The sixth aspect of the technical scheme of the invention also provides 4-allyl-2-amino-6- (benzofuran-5-yl) phenol shown in a chemical structural formula III:
the seventh aspect of the present invention provides the process for producing 4-allyl-2-amino-6- (benzofuran-5-yl) phenol according to the sixth aspect, characterized in that it comprises the following reaction:
wherein, the reduction reaction is selected as follows: chemical reduction or catalytic hydrogenation reduction; chemical reduction of the selected reducing agent: zinc powder-ammonium chloride, tin chloride, iron powder-hydrochloric acid, sodium dithionate, potassium dithionate, sodium sulfite or sodium sulfide; the catalytic hydrogenation reduction selects nickel catalytic reduction or palladium catalytic reduction.
The beneficial technical effects are as follows:
the 8- (benzofuran-5-yl) benzoxazinone derivatives of the present invention are a new class of compounds with insecticidal activity.
Detailed Description
The following examples are intended to illustrate the invention without further limiting it.
Example 1
Preparation of 4-allyl-2- (2-methylbenzofuran-5-yl) phenol
15mmol of honokiol and 0.225mmol of PdCl21.5mmol of NaOAc with 56mL of DMA/H2Dissolving O (6:1), charging 8atm O into the autoclave2And reacting for 16 hours in an oil bath at the temperature of 60 ℃. After the reaction, the reaction mixture was transferred to a separatory funnel and 100mL of H was added2Diluting with O, extracting with ethyl acetate for 3 times, mixing organic layers, and extracting with anhydrous Na2SO4Drying and rotary evaporating to recover solvent. Purifying the crude product by column chromatography to obtain yellow oily liquid 4-allyl-2- (2-methylbenzofuran-5-yl) phenol with the yield of 86%;1H NMR(400MHz，CDCl3) δ: 7.53(d, J ═ 1.5Hz, 1H, benzofuran ring 4-H), 7.50(d, J ═ 8.4Hz, 1H, benzofuran ring 7-H), 7.26(dd, J ═ 8.4, 1.5Hz, 1H, benzofuran ring 6-H), 7.10 to 7.07(m, 2H, C)6H3 3,5-H)，6.94(d，1H，J＝8.8Hz，C6H36-H), 6.41(s, 1H, benzofuran ring 3-H), 6.04-5.93 (m, 1H, CH), 5.21(s, 1H, OH), 5.12 ℃; E5.04(m，2H，＝CH2)，3.36(d，J＝6.7Hz，2H，CH2)，2.49(s，3H，CH3)；13C NMR(101MHz，CDCl3)δ：156.58，154.44，151.10，138.08，132.29，131.79，130.83，130.21，129.00，128.75，124.43，120.87，115.98，115.75，111.34，102.93，39.61，14.19。
Example 2
Preparation of 4-allyl-2-nitroso-6- (2-methylbenzofuran-5-yl) phenol
Dissolving 10mmol of 4-allyl-2- (2-methylbenzofuran-5-yl) phenol and 15mmol of sodium nitrite in 25mL of acetonitrile and 5mL of water, dropwise adding 3mL of concentrated hydrochloric acid (36-38%) at room temperature, continuing to react for 0.5h after about 1h of dropwise addition, and completely detecting by TLC (thin layer chromatography); quenching by adding water, extracting by dichloromethane, drying an organic phase by using anhydrous sodium sulfate, and purifying by column chromatography to obtain a yellow solid 4-allyl-2-nitroso-6- (2-methylbenzofuran-5-yl) phenol with the yield of 76.9 percent; mp.58-60 ℃;1H NMR(400MHz，CDCl3)δ：11.04(s，1H，OH)，7.93(d，J＝2.2Hz，1H，C6H25-H), 7.63(d, J ═ 1.7Hz, 1H, benzofuran ring 4-H), 7.50(d, J ═ 2.2Hz, 1H, C)6H23-H), 7.47(d, J ═ 8.5Hz, 1H, benzofuran ring 7-H), 7.36(dd, J ═ 8.5, 1.7Hz, 1H, benzofuran ring 6-H), 6.41(s, 1H, benzofuran ring 3-H), 5.96(ddt, J ═ 17.2, 10.7, 6.7Hz, 1H, CH), 5.18 to 5.11(m, 2H, ═ CH)2)，3.41(d，J＝6.7Hz，2H，CH2)，2.48(s，3H，CH3)；13C NMR(101MHz，CDCl3)δ：156.34，154.51，151.41，139.42，136.07，133.88，133.53，131.78，130.31，129.38，124.61，123.07，121.10，117.17，110.43，102.75，38.96，14.15。
Example 3
Preparation of 4-allyl-2-amino-6- (2-methylbenzofuran-5-yl) phenol
5.0mmol 4-allyl-2-nitroso-6- (2-methylbenzofuran-5-yl) phenol and 1.0mmol ammonium chloride were dissolved in 50mL ethanol and 10mL water, 25mmol zinc powder and 2.5mL acetic acid were added, and the reaction was carried out at room temperature for 0.5 h. Filtering, diluting the filtrate with water, extracting with ethyl acetate, drying the organic phase with anhydrous sodium sulfate, and purifying by column chromatography to obtain brown solid 4-allyl-2-amino-6- (2-methylbenzofuran-5-yl) phenol with yield of 73.2%; mp.80-82 ℃;1H NMR(400MHz，DMSO-d6) δ: 7.56(s, 1H, benzofuran ring 4-H), 7.46(d, J ═ 8.5Hz, 1H, benzofuran ring 7-H), 7.29(d, J ═ 8.5Hz, 1H, benzofuran ring 6-H), 6.58(s, 1H, C)6H2)，6.46(s，1H，C6H2) 6.31(s, 1H, benzofuran ring 3-H), 5.98 to 5.87(m, 1H, CH), 5.07(d, J ═ 17.0Hz, 1H, ═ CH2)，5.00(d，J＝10.0Hz，1H，＝CH2)，4.72(br，1H)，3.20(d，J＝6.7Hz，2H，CH2)，2.45(s，3H，CH3)；13C NMR(101MHz，DMSO-d6)δ：155.97，153.57，138.97，138.87，138.82，134.47，131.91，130.42，129.11，125.16，121.06，118.96，115.56，114.34，110.29，103.34，14.26。
Example 4
Preparation of 6-allyl-8- (2-methylbenzofuran-5-yl) -2H-benzo [ b ] [1,4] oxazin-3 (4H) -one
1.0mmol of 4-allyl-2-amino-6- (2-methylbenzofuran-5-yl) phenol, 5mL of tetrahydrofuran, 2.5mmol of triethylamine and 0.2mmol of 4-dimethylaminopyridine were added dropwise to a solution of 1.0mmol of chloroacetyl chloride in 1mL of dichloromethane with stirring at room temperature, after completion of the addition for 10 min. Heating to reflux and reacting for 12 h. The reaction solution is desolventized and purified by column chromatography to obtain white solid 6-allyl-8- (2-methylbenzofuran)-5-yl) -2H-benzo [ b][1,4]Oxazin-3 (4H) -ketone, yield 63.8%, mp.169-171 ℃;1H NMR(400MHz，DMSO-d6) δ 10.72(s, 1H, NH), 7.62(s, 1H, benzofuran ring 4-H), 7.51(d, J ═ 8.5Hz, 1H, benzofuran ring 7-H), 7.33(d, J ═ 8.5Hz, 1H, benzofuran ring 6-H), 6.84(s, 1H, C)6H2)，6.73(s，1H，C6H2) 6.60(s, 1H, benzofuran ring 3-H), 5.95(ddt, J ═ 17.0, 9.7, 6.7Hz, 1H, CH), 5.12(d, J ═ 17.0Hz, 1H, ═ CH2)，5.06(d，J＝9.7Hz，1H，＝CH2)，4.54(s，2H，OCH2)，3.33(d，J＝6.7Hz，1H，CH2)，2.46(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)δ165.89，156.43，153.93，139.24，138.07，134.40，131.93，130.32，129.25，128.52，125.01，124.86，121.14，116.42，115.21，110.55，103.32，67.32，39.31，14.25。
Example 5
Preparation of 6-allyl-8- (2-methylbenzofuran-5-yl) -2-methylbenzo [ b ] [1,4] oxazin-3 (4H) -one
1.0mmol 4-allyl-2-amino-6- (2-methylbenzofuran-5-yl) phenol, 5mL tetrahydrofuran, 2.5mmol triethylamine and 0.2mmol 4-dimethylaminopyridine, 1mL tetrahydrofuran solution containing 1.0mmol 2-chloropropionyl chloride was added dropwise with stirring at room temperature, after 10 min. Heating to reflux and reacting for 12 h. The reaction solution is desolventized and purified by column chromatography to obtain 6-allyl-8- (2-methylbenzofuran-5-yl) -2-methylbenzo [ b ] [1,4] oxazine-3 (4H) -ketone.
Example 6
Pesticidal activity of 8- (benzofuran-5-yl) benzoxazinone derivatives
1 test target
Armyworm (Mythimna sepatara) line was raised with fresh corn leaves for years of sensitive lines; the test insects are 3-instar larvae; the test insects were healthy adult mites.
2 culture conditions
The culture conditions of the test target and the post-test target are 25 + -5 deg.C, 65 + -5% relative humidity, and 12/12h (L/D) of light period.
3 test agents (technical): 8- (benzofuran-5-yl) benzoxazinone derivatives.
4, preparing a raw medicine by using the medicine: weighing the required amount by using a ten-thousandth electronic balance; solvent: n, N Dimethylformamide (DMF), 0.2%; emulsifier: tween 80, 0.2%; adding clear water to dilute to the required concentration.
5 test methods refer to "evaluation of biological Activity of pesticides SOP".
Common sieve for armyworm: the spraying method is adopted. Corn leaf segments with basically consistent sizes are placed in a culture dish (phi 90mm) filled with filter paper, 10 heads of third-instar larvae are inoculated, and the culture dish is placed under a Potter spray tower for spraying. The amount of spray was 1 ml/10-head, 2 times repeated. After the treatment, the culture medium is placed in an observation room for culture. And observing at regular time. After 72h, the mortality was checked and documented and the mortality was calculated.
6 poisoning Activity
The poisoning activity of preferred compounds: when the concentration of the active ingredients is 500mg/L, the death rate of the 6-allyl-8- (2-methylbenzofuran-5-yl) -2H-benzo [ b ] [1,4] oxazine-3 (4H) -ketone on armyworm is 80.0% after 72 hours of application.
The 8- (benzofuran-5-yl) benzoxazinone derivative has good insecticidal activity and can be used for preparing insecticides for agricultural application.
Claims (7)
1. A class of 8- (benzofuran-5-yl) benzoxazinone derivatives represented by the chemical structural formula I:
wherein R is selected from: hydrogen, C1～C2Alkyl radical, C3～C4Straight-chain or branched alkyl radicals, R1Selected from: c1～C3A linear alkyl group.
2. A preparation method of 8- (benzofuran-5-yl) benzoxazinone derivatives shown in a chemical structural formula I is characterized by comprising the following preparation reactions:
wherein R and R1 are as defined in claim 1.
3. Use of the 8- (benzofuran-5-yl) benzoxazinone derivative according to claim 1 for the preparation of a pesticide.
4. A class of 4-allyl-2-nitroso-6- (benzofuran-5-yl) phenols having the chemical formula ii:
wherein R is selected from: hydrogen, C1～C2Alkyl radical, C3～C4Straight chain alkyl or branched alkyl.
5. A process for the preparation of 4-allyl-2-nitroso-6- (benzofuran-5-yl) phenol according to claim 4, characterized in that it is prepared by the following reaction:
wherein R is as defined in claim 4; the nitrosation agent selected in the nitrosation reaction is nitrous acid or sodium nitrite and concentrated hydrochloric acid, and the concentration of the concentrated hydrochloric acid is 36-38%; the feeding ratio of the 4-allyl-2- (2-methylbenzofuran-5-yl) phenol to the sodium nitrite is 1.0: 1.1-1.5, carrying out nitrosation reaction in acetonitrile and water.
6. A class of 4-allyl-2-amino-6- (benzofuran-5-yl) phenols represented by the chemical structural formula iii:
wherein R is selected from: hydrogen, C1～C2Alkyl radical, C3～C4Straight chain alkyl or branched alkyl.
7. The process for the preparation of 4-allyl-2-amino-6- (benzofuran-5-yl) phenol according to claim 6, characterized in that it is prepared by the following reaction:
wherein R is as defined in claim 6; and (3) selection of reduction reaction: chemical reduction or catalytic hydrogenation reduction; chemical reduction of the selected reducing agent: zinc powder-ammonium chloride, tin chloride, iron powder-hydrochloric acid, sodium dithionate, potassium dithionate, sodium sulfite or sodium sulfide; the catalytic hydrogenation reduction selects nickel catalytic reduction or palladium catalytic reduction.
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| CN1835954A (en) * | 2003-08-14 | 2006-09-20 | 拜尔农作物科学股份公司 | 4-biphenyl-substituted 4-substituted pyrazolidin-3,5-diones pesticide agent and/or microbicide and/or herbicide |
| CN1863806A (en) * | 2003-08-14 | 2006-11-15 | 拜尔农作物科学股份公司 | 4-biphenylsubstituted pyrazolidin-3,5-dione derivatives |
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