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WO2004087694A1 - A heterocycle-substituted benzoxazine compounds having bioactivity - Google Patents

A heterocycle-substituted benzoxazine compounds having bioactivity Download PDF

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Publication number
WO2004087694A1
WO2004087694A1 PCT/CN2003/000501 CN0300501W WO2004087694A1 WO 2004087694 A1 WO2004087694 A1 WO 2004087694A1 CN 0300501 W CN0300501 W CN 0300501W WO 2004087694 A1 WO2004087694 A1 WO 2004087694A1
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Prior art keywords
substituted benzoxazine
het
compounds
ch2c
benzoxazine ring
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French (fr)
Chinese (zh)
Inventor
Zhongke Hou
Yeguo Ren
Mingzhi Huang
Manxiang Lei
Xiaoming Ou
Kaibao Zang
Xiaoguang Wang
Aiping Liu
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Hunan Research Institute of Chemical Industry
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Hunan Research Institute of Chemical Industry
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • 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

Definitions

  • the invention relates to a biologically active heterocyclic substituted benzoxazine ring compound and a preparation method thereof. Background technique
  • the object of the present invention is to provide a biologically active heterocyclic substituted benzoxazine ring compound represented by the general formula (I) and a preparation method thereof.
  • the general formula (I) of the present invention is as follows: t
  • X is F, CI, CH 3 , CF 3 , CN;
  • R 2 is H, CH 3 , Ph
  • R is F, CI, Br, CH 3 , N0 2 ;
  • n represents the number of substituents, optionally 0, 1, 2, 3, 4;
  • R 1 is only CH 2 C ⁇ CI.
  • Compound (C) is reacted by adding an acid-binding agent and a halide in an appropriate solvent to obtain the target compound of general formula (I).
  • the better solvent is DMF
  • the better acid-binding agent is NaH
  • Compound (E) is added to a suitable solvent containing reduced iron powder, heated to 30 ° C to 120 ° C, and stirred for 1 hour to 12 hours to obtain (F).
  • the heterocyclic substituted benzoxazine ring compounds of the general formula (I) of the present invention have very good biological activity, and the herbicidal activity of some compounds is better than the current one.
  • the conventional herbicide used when applied at a low dose of 18.75ga.i / ha, has a 90% control effect on most broad-leaved weeds and is safer for crops such as stalks, corn, rice, and soybeans. detailed description
  • Example 1 Preparation of the 120th compound N- (7-fluoro-3-oxo 4-propynyl-1,4-benzoxazinone-6-yl) phthalimide (NO .120).
  • reaction formula is:
  • Dicotyledon choose Chenopodium album, Ramie (Abutilon theophrast) i, concave head wide
  • the growth inhibition rate (%) 100 (control plant height-treated plant height) I control plant height.
  • the herbicidal activity is graded: A-level growth inhibition rate> 90%; B-level growth inhibition rate 75 90%; C-level growth inhibition rate 50 ⁇ 75%; D-level growth inhibition rate is less than 50%.
  • Some compounds of the present invention such as compounds N0.69, 120, 137, and 626, were used to treat stem and leaves of potted test plants after buds at an application rate of 18.75ga.i / ha.
  • Compound NO. 120 is safe for sorghum at a dose of 37.5ga.i / ha; it is safe for rice, corn, and soybeans at a lower dose of 18.75ga.i / ha. But it is not safe for rapeseed and wheat.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Secondary Cells (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention disclose a Heterocycle-substituted benzoxazine compounds of formula (I) and the process for preparing them: Wherein: Het is: (II) Y is O, S; w is 0,1; X is F, Cl, CH3, CF3, CN; R2 is H, CH3, Ph; R is F, Cl, Br, CH3, NO2; m represents the number of the substituents, and selected from 0, 1, 2, 3, 4; When Het is (II), R1 is CH3, CHF2, CH2CH3, CH2CN, CH2CH2CH3, CH2CH=CH2, CH2C≡CH, CH2C≡C-Br, CH2C≡C-Cl, CH2C≡C-I, CH2OCH2CH3; When Het is (III), R1 is CH2C≡C-I only ° The compounds of the present invention have excellent herbicidal activity, when used at low dosage as 18.75 ga.i/ha, a part of the compounds have effect ≥ 90% against most broad-leaved weeds, and they are safe to the crops such as sorghum, maize, rice plant, soyabean, etc.

Description

种具有生物活性的杂环取代笨并噁嗪环 技术领域  Biologically active heterocyclic substituted benzoxazine ring TECHNICAL FIELD

本发明涉及一种具有生物活性的杂环取代的苯并噁嗪环类化合物及其制备方法。 背景技术  The invention relates to a biologically active heterocyclic substituted benzoxazine ring compound and a preparation method thereof. Background technique

据文献报道 1,2,4,5-四取代苯类化合物是一种原卟啉原氧化酶抑制剂， 具有除草活 性。 其中稠杂环四取代苯类化合物更具生物活性， 国外已有不少专利报导。 例如： EP420194、 USP5084084、 USP5127935 > USP5322835、 USP6323154、 DE3922107、 JP03,47180、 USP5232898、 JP62277383、 EP362615等报导了很多稠杂环四取代苯类化 合物及其复配制剂具有除草活性。 其中化合物 (flumioxazin)已经商品化。  It is reported in the literature that 1,2,4,5-tetra-substituted benzene compounds are protoporphyrinogen oxidase inhibitors and have herbicidal activity. Among them, fused heterocyclic tetra-substituted benzene compounds are more biologically active, and many patents have been reported abroad. For example: EP420194, USP5084084, USP5127935> USP5322835, USP6323154, DE3922107, JP03,47180, USP5232898, JP62277383, EP362615, etc. reported that many fused heterocyclic tetra-substituted benzene compounds and their formulations have herbicidal activity. Among them, the compound (flumioxazin) has been commercialized.

Figure imgf000003_0001
Figure imgf000003_0001

Flumioxazin Flumioxazin

此外专利 US5696056、 JP2001-328911报道如下结构化合物及其制剂也具有除草活  In addition, patents US5696056 and JP2001-328911 report that the following structural compounds and their preparations also have herbicidal activity

Figure imgf000003_0002
Figure imgf000003_0002

上述各种取代稠杂环衍生物均具有不同程度的除草活性，但有的对阔叶草的选择性 除草效果较差， 用于水稻、 小麦、玉米、大豆等作物除草时， 会对作物本身造成一定的 伤害；有的仅适用于作物的芽前处理，对生长期内杂草防效较差；还有的内吸传导作用 较差， 对大齡杂草防效较差。  The above-mentioned various substituted fused heterocyclic derivatives all have different degrees of herbicidal activity, but some have a poor selective herbicidal effect on broadleaf. When used for weeding crops such as rice, wheat, corn, soybean, etc., they will affect the crop itself. Causes certain damage; some are only suitable for pre-emergence treatment of crops, which have a poor control effect on weeds during the growing period; others have a poor systemic conduction effect and have a poor control effect on older weeds.

发明内容  Summary of the Invention

本发明的目的是提供用结构通式 （I)表示的具有生物活性的杂环取代的苯并噁嗪 环类化合物及其制备方法， 本发明的结构通式（I)如下： t The object of the present invention is to provide a biologically active heterocyclic substituted benzoxazine ring compound represented by the general formula (I) and a preparation method thereof. The general formula (I) of the present invention is as follows: t

Figure imgf000003_0003
Figure imgf000003_0003

( I ) I )中 Het为： (I) I) Het is:

Figure imgf000004_0001
Figure imgf000004_0001

(Π) (ΠΙ) (Π) (ΠΙ)

Υ=0， S;  Υ = 0, S;

W=0, 1； W = 0, 1;

X为 F， CI, CH3， CF3， CN; X is F, CI, CH 3 , CF 3 , CN;

R2为 H， CH3, Ph; R 2 is H, CH 3 , Ph;

R为 F， CI, Br, CH3， N02; R is F, CI, Br, CH 3 , N0 2 ;

m表示取代基的数目， 可选 0， 1， 2， 3， 4； m represents the number of substituents, optionally 0, 1, 2, 3, 4;

当 Het= (II)时， R1为 CH3， CHF2， CH2CH3, C¾CN, CH2CH2C¾， CH2CH=CH2，When Het = (II), R 1 is CH 3 , CHF 2 , CH 2 CH 3 , C¾CN, CH 2 CH 2 C¾, CH 2 CH = CH 2 ,

CH2C≡CH， CH2C≡C-Br, CH2C≡C-C1, CH2C≡C-L CH2OC¾CH3, CH 2 C≡CH, CH 2 C≡C-Br, CH 2 C≡C-C1, CH 2 C≡CL CH 2 OC¾CH 3 ,

当 Het= (ΠΙ)时， R1仅为 CH2C≡C-I。 When Het = (ΠI), R 1 is only CH 2 C≡CI.

本发明结构通式（I)化合物的制备方法如下： The preparation method of the compound of the general formula (I) of the present invention is as follows:

Figure imgf000004_0002
Figure imgf000004_0002

Figure imgf000005_0001
Figure imgf000005_0001

中间体（A)在适当溶剂中， 加入相应的取代（氢化）苯酐（B)， 加热至 30°C~150 Intermediate (A) in a suitable solvent, add the corresponding substituted (hydrogenated) phthalic anhydride (B), and heat to 30 ° C ~ 150

V， 搅拌反应 1 小时〜 12小时得到 （C)。 其中较好的溶剂是冰乙酸； 较好的摩尔比为 1:1.2； 较佳的温度是溶剂回流温度； 较优的反应时间为 3小时。 V, Stir the reaction for 1 to 12 hours to obtain (C). The preferred solvent is glacial acetic acid; the preferred molar ratio is 1: 1.2; the preferred temperature is the reflux temperature of the solvent; the preferred reaction time is 3 hours.

化合物（C)在适当溶剂中加入缚酸剂和卤化物反应得到目标通式（I)化合物。其 中较好的溶剂是 DMF;较好的缚酸剂是 NaH;较好的摩尔比是（C): 卤化物： NaH=l:l: Compound (C) is reacted by adding an acid-binding agent and a halide in an appropriate solvent to obtain the target compound of general formula (I). Among them, the better solvent is DMF; the better acid-binding agent is NaH; the better molar ratio is (C): halide: NaH = l: l:

1.2； 较佳的温度 25°C ; 较优的反应时间 8小时。 1.2; Better temperature 25 ° C; Better reaction time 8 hours.

中间体 （A) 的合成参考文献 US4734124方法如下：  The synthesis reference of intermediate (A) US4734124 is as follows:

Figure imgf000005_0002
Figure imgf000005_0002

( F) ( G ) (A) 原料（D)在适当溶剂中， 加入溴乙酸乙酯和缚酸剂， 加热至 30~150°C， 搅拌反应 1~12小时得到 （E)。 其中较好的溶剂是丙酮； 较好的缚酸剂是 K2C03 ; 较好的摩尔比 为原料（D): 溴乙酸乙酯： 缚酸剂 =1: 1:1.5； 较佳的温度是溶剂回流温度； 较优的反应 时间为 3小时。 (F) (G) (A) The raw material (D) is added to a suitable solvent, ethyl bromoacetate and an acid binding agent are added, and the mixture is heated to 30 to 150 ° C and stirred for 1 to 12 hours to obtain (E). Among them, the preferred solvent is acetone; the preferred acid binding agent is K 2 C0 3; the preferred molar ratio is the raw material (D): ethyl bromoacetate: the acid binding agent = 1: 1: 1.5; the preferred temperature Is the solvent reflux temperature; the preferred reaction time is 3 hours.

化合物（E)加入到含还原铁粉的适当溶剂中， 加热至 30°C~120°C， 搅拌反应 1小 时~12小时得到（F)。其中较好的溶剂是冰乙酸； 较好的摩尔比为原料（E): 还原铁粉 =1: 5； 较佳的温度是 80Ό ; 较优的反应时间为 3小时。  Compound (E) is added to a suitable solvent containing reduced iron powder, heated to 30 ° C to 120 ° C, and stirred for 1 hour to 12 hours to obtain (F). Among them, the preferred solvent is glacial acetic acid; the preferred molar ratio is raw material (E): reduced iron powder = 1: 5; the preferred temperature is 80 ° C; the preferred reaction time is 3 hours.

化合物 （F)加入到 80%硫酸中， 冷却到 0°C， 滴加 60%的硝酸， 硝化反应一定时 间得到 （G), 其在冰乙酸中用还原铁粉还原得到中间体（A)。 依据上述制备方法， 合成了一系列本发明的杂环取代的苯并噁嗪环类化合物， 具 体见下表。Compound (F) is added to 80% sulfuric acid, cooled to 0 ° C, and 60% nitric acid is added dropwise to obtain (G) by a nitration reaction for a certain time, which is reduced with reduced iron powder in glacial acetic acid to obtain intermediate (A). According to the above preparation method, a series of heterocyclic substituted benzoxazine ring compounds of the present invention are synthesized, as shown in the following table.

Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000008_0001
Figure imgf000009_0001
Figure imgf000010_0001
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000008_0001
Figure imgf000009_0001
Figure imgf000010_0001

Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
NO W Y X R2 R1
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
NO WYXR 2 R 1

415 1 0 F CH3 C¾C≡C-I 3-C1415 1 0 F CH 3 C¾C≡CI 3-C1

416 1 0 F CH3 C¾C≡C-I 3-Br416 1 0 F CH 3 C¾C≡CI 3-Br

417 1 0 F C¾ 3-F417 1 0 F C¾ 3-F

418 1 0 F CH3 CH2C≡C-I 3- CH3 418 1 0 F CH 3 CH 2 C≡CI 3- CH 3

419 1 0 F CH3 CH2C≡C-I 3-N02 419 1 0 F CH 3 CH 2 C≡CI 3-N0 2

420 1 0 F CH3 CH2C≡C-I 4-F420 1 0 F CH 3 CH 2 C≡CI 4-F

421 1 0 F C¾ CH2C≡C-I 4-C1421 1 0 F C¾ CH 2 C≡CI 4-C1

422 1 0 F C¾ CH2C≡C-I 4-Br422 1 0 F C¾ CH 2 C≡CI 4-Br

423 1 0 F CH3 CH2C≡C-I 4- CH3423 1 0 F CH 3 CH 2 C≡CI 4- CH3

424 1 0 F CH3 CH2C≡C-I 4-NO2424 1 0 F CH 3 CH 2 C≡CI 4-NO2

425 1 0 F CH3 CH2C≡C-I 3,6-2 CI425 1 0 F CH 3 CH 2 C≡CI 3,6-2 CI

426 1 0 F CH3 CH2C≡C-I 3,6-2 F426 1 0 F CH 3 CH 2 C≡CI 3,6-2 F

427 1 0 F C¾ CH2C≡C-I 4,5-2 CI427 1 0 F C¾ CH 2 C≡CI 4,5-2 CI

428 1 0 F CH3 CH2C≡C-I 3,4,5,6,-4Cl428 1 0 F CH 3 CH 2 C≡CI 3,4,5,6, -4Cl

429 1 0 F CH3 CH2C≡C-I 3,4,5,6,-4F429 1 0 F CH 3 CH 2 C≡CI 3,4,5,6, -4F

430 1 0 F CH3 CH2C≡C-I 3,4,5，6,-4Br430 1 0 F CH 3 CH 2 C≡CI 3,4,5,6, -4Br

431 1 0 F C¾ CH2C 〇≡C-C1 ―431 1 0 F C¾ CH 2 C 〇≡C-C1 ―

432 1 0 F CH3 CH2C≡C-C1 3-C1432 1 0 F CH 3 CH 2 C≡C-C1 3-C1

433 1 0 F CH3 CH2C≡C-C1 3-Br433 1 0 F CH 3 CH 2 C≡C-C1 3-Br

434 1 0 F CH3 CH2C≡C-C1 3-F434 1 0 F CH 3 CH 2 C≡C-C1 3-F

435 1 0 F CH3 CH2C≡C-C1 3- CH3435 1 0 F CH 3 CH 2 C≡C-C1 3- CH3

436 1 0 F CH3 CH2C≡C-C1 3-NO2436 1 0 F CH 3 CH 2 C≡C-C1 3-NO2

437 1 0 F CH3 CH2C≡C-C1 4-F437 1 0 F CH 3 CH 2 C≡C-C1 4-F

438 1 0 F CH3 CH2C≡C-C1 4-C1438 1 0 F CH 3 CH 2 C≡C-C1 4-C1

439 1 0 F CH3 CH2C≡C-C1 4-Br439 1 0 F CH 3 CH 2 C≡C-C1 4-Br

440 1 0 F CH3 CH2C≡C-C1 4- CH3 440 1 0 F CH 3 CH 2 C≡C-C1 4- CH 3

441 1 0 F CH3 CH2C≡C-C1 4-N02 441 1 0 F CH 3 CH 2 C≡C-C1 4-N0 2

442 1 0 F CH3 CH2C≡C-C1 3,6-2 CI442 1 0 F CH 3 CH 2 C≡C-C1 3,6-2 CI

443 1 0 F CH3 CH2C≡C-C1 3,6-2 F443 1 0 F CH 3 CH 2 C≡C-C1 3,6-2 F

444 1 0 F CH3 CH2C≡C-C1 4,5-2 CI444 1 0 F CH 3 CH 2 C≡C-C1 4,5-2 CI

445 1 0 F CH3 CH2C≡C-C1 3,4,5,6,-^1445 1 0 F CH 3 CH 2 C≡C-C1 3,4,5,6,-^ 1

446 1 0 F CH3 CH2C≡C-C1 3,4,5,6,-4F446 1 0 F CH 3 CH 2 C≡C-C1 3,4,5,6, -4F

447 1 0 F CH3 CH2C≡C-C1 3,4，5,6,-4Br447 1 0 F CH 3 CH 2 C≡C-C1 3,4,5,6, -4Br

448 1 0 F CH3 CH2C≡C-Br ―448 1 0 F CH 3 CH 2 C≡C-Br ―

449 1 0 F CH3 CH2C≡C-Br 3-C1449 1 0 F CH 3 CH 2 C≡C-Br 3-C1

450 1 0 F CH3 CH2C≡C-Br 3-Br450 1 0 F CH 3 CH 2 C≡C-Br 3-Br

451 1 0 F CH3 CH2C≡C-Br 3-F451 1 0 F CH 3 CH 2 C≡C-Br 3-F

452 1 0 F CH3 CH2C≡C-Br _3- CH3 452 1 0 F CH 3 CH 2 C≡C-Br _3- CH 3

453 1 0 F CH3 CH2C≡C-Br 3-N02 453 1 0 F CH 3 CH 2 C≡C-Br 3-N0 2

454 1 0 F CH3 CH2C≡C-Br 4-F454 1 0 F CH 3 CH 2 C≡C-Br 4-F

455 1 0 F CH3 CH2C≡C-Br 4-C1455 1 0 F CH 3 CH 2 C≡C-Br 4-C1

456 1 0 F . CH3 CH2C≡C-Br 4-Br 456 1 0 F. CH 3 CH 2 C≡C-Br 4-Br

Figure imgf000015_0001
Figure imgf000016_0001
NO W Y X R2 R1
Figure imgf000015_0001
Figure imgf000016_0001
NO WYXR 2 R 1

540 1 0 CI CH3 CH2OCH2CH3 4-F540 1 0 CI CH 3 CH2OCH2CH3 4-F

541 1 0 CI CH3 CH2CH=CH2 4-F541 1 0 CI CH 3 CH 2 CH = CH 2 4-F

542 1 0 CI CH3 C¾C≡CH 4-F542 1 0 CI CH 3 C¾C≡CH 4-F

543 1 0 CI CH3 CH2C≡C-I 4-F543 1 0 CI CH 3 CH 2 C≡CI 4-F

544 1 0 CI CH3 CH2C≡C-C1 4-F544 1 0 CI CH 3 CH 2 C≡C-C1 4-F

545 1 0 CI CH3 CH2C≡C-Br 4-F545 1 0 CI CH 3 CH 2 C≡C-Br 4-F

546 1 0 CI CH3 CH3 3，4,5,6,-4F546 1 0 CI CH 3 CH 3 3, 4, 5, 6, 4F

547 1 0 CI CH3 CHF2 3，4,5,6,-4F547 1 0 CI CH 3 CHF 2 3, 4, 5, 6, 4F

548 1 0 CI CH3 CH2CN 3,4,5,6,-4F548 1 0 CI CH 3 CH 2 CN 3,4,5,6, -4F

549 1 0 CI C¾ CH2CH3 3,4,5,6,-4F549 1 0 CI C¾ CH2CH3 3,4,5,6, -4F

550 1 0 CI CH3 CH2CH2CH3 3,4,5,6,-4F550 1 0 CI CH 3 CH2CH2CH3 3,4,5,6, -4F

551 1 0 CI CH3 CH2OCH2CH3 3,4,5,6,-4F551 1 0 CI CH 3 CH 2 OCH 2 CH 3 3,4,5,6, -4F

552 1 0 CI CH3 CH2CH=C¾ 3,4,5,6,-4F552 1 0 CI CH 3 CH 2 CH = C¾ 3,4,5,6, -4F

553 1 0 CI CH3 C¾C≡CH 3,4,5,6,-4F553 1 0 CI CH 3 C¾C≡CH 3,4,5,6, -4F

554 1 0 CI CH3 CH2C≡C-I 3,4,5,6,-4F554 1 0 CI CH 3 CH 2 C≡CI 3,4,5,6, -4F

555 1 0 CI CH3 CH2C≡C-C1 3,4,5,6,-4F555 1 0 CI CH 3 CH 2 C≡C-C1 3,4,5,6, -4F

556 1 0 CI CH3 CH2C≡C-Br 3,4,5,6,-4F556 1 0 CI CH 3 CH 2 C≡C-Br 3,4,5,6, -4F

557 1 s F H CH3 一557 1 s FH CH 3

558 1 s F H CHF2 一558 1 s FH CHF 2

559 1 s F H CH2CN 一559 1 s FH CH 2 CN 1

-560 1 s F ^ H C¾CH3 一-560 1 s F ^ H C¾CH 3

561 1 s F H CH2CH2CH3 一561 1 s FH CH 2 CH 2 CH 3

562 1 s F H CH2OCH2CH3 一562 1 s FH CH 2 OCH 2 CH 3

563 1 s F H CH2CH=CH2 一563 1 s FH CH 2 CH = CH 2

564 1 s F H C¾C≡CH 一564 1 s F H C¾C≡CH 1

565 1 s F H CH2C≡C-I 一565 1 s FH CH 2 C≡CI 1

566 1 s F H CH2C≡C-C1 一566 1 s FH CH 2 C≡C-C1 a

567 1 s F H C¾C≡C-Br 一567 1 s F H C¾C≡C-Br 1

568 1 s F CH3 CH3 一568 1 s F CH 3 CH 3

569 1 s F CH3 CHF2 一569 1 s F CH 3 CHF 2

570 1 s F C¾ CH2CN 一570 1 s F C¾ CH 2 CN 1

571 1 s F CH3 CH2CH3 一571 1 s F CH 3 CH2CH3 a

572 1 s F CH3 CH2CH2C¾ 一572 1 s F CH 3 CH 2 CH 2 C¾ a

573 1 s F CH3 CH2OCH2CH3 一573 1 s F CH 3 CH 2 OCH 2 CH 3

574 1 s F CH3 CH2CH=CH2 一574 1 s F CH 3 CH 2 CH = CH 2

575 1 s F CH3 CH2C≡CH 一575 1 s F CH 3 CH 2 C≡CH 1

576 1 s F CH3 C¾C≡C-I 一576 1 s F CH 3 C¾C≡CI 1

577 1 s F CH3 CH2C≡C-C1 一577 1 s F CH 3 CH 2 C≡C-C1 a

578 1 s F CH3 CH2C≡C-Br 一578 1 s F CH 3 CH 2 C≡C-Br 1

579 0 0 F H CH3 一579 0 0 FH CH 3

580 0 0 F H CHF2 一580 0 0 FH CHF 2

581 0 0 F H CH2CN 一

Figure imgf000018_0001
Figure imgf000019_0001
581 0 0 FH CH 2 CN 1
Figure imgf000018_0001
Figure imgf000019_0001

Figure imgf000019_0002
NO W Y X R2 R1
Figure imgf000019_0002
NO WYXR 2 R 1

663 0 0 F H C¾C≡C-I 3-F 663 0 0 F H C¾C≡C-I 3-F

664 0 0 F H CH2C≡C-I 4-F664 0 0 FH CH 2 C≡CI 4-F

665 0 0 F CH3 CH2C≡C-I 一 665 0 0 F CH 3 CH 2 C≡CI 1

666 0 0 F C¾ CH2C≡C-I 3-F666 0 0 F C¾ CH 2 C≡CI 3-F

667 0 0 F CH3 CH2C≡C-I 4-F 667 0 0 F CH 3 CH 2 C≡CI 4-F

668 0 0 CI H CH2C≡C-I 一 668 0 0 CI H CH 2 C≡CI 1

669 0 0 CI H CH2C≡C-I 3-F 669 0 0 CI H CH 2 C≡CI 3-F

670 0 0 CI H CH2C≡C-I 4-F 670 0 0 CI H CH 2 C≡CI 4-F

671 0 0 CI CH3 CH2C≡C-I 一 671 0 0 CI CH 3 CH 2 C≡CI 1

672 0 0 CI CH3 CH2C≡C-I 3-F 672 0 0 CI CH 3 CH 2 C≡CI 3-F

673 0 0 CI CH3 CH2C≡C-I 4-F 673 0 0 CI CH 3 CH 2 C≡CI 4-F

674 0 0 F H CH2C≡C-I 一 674 0 0 FH CH 2 C≡CI I

675 0 0 F H CH2C≡C-I 3-F 675 0 0 FH CH 2 C≡CI 3-F

676 0 0 F H CH2C≡C-I 4-F 676 0 0 FH CH 2 C≡CI 4-F

677 0 0 F CH3 CH2C≡C-I 一 677 0 0 F CH 3 CH 2 C≡CI One

678 0 0 F CH3 CH2C≡C-I 3-F 678 0 0 F CH 3 CH 2 C≡CI 3-F

679 0 0 F C¾ CH2C≡C-I 4-F 679 0 0 F C¾ CH 2 C≡CI 4-F

680 0 0 CI H CH2C≡C-I 一 680 0 0 CI H CH 2 C≡CI 1

681 0 0 CI H CH2C≡C-I 3-F 681 0 0 CI H CH 2 C≡CI 3-F

682 0 0 CI H CH2C≡C-I 4-F 682 0 0 CI H CH 2 C≡CI 4-F

683 0 0 CI CH3 CH2C≡C-I 一 683 0 0 CI CH 3 CH 2 C≡CI 1

684 0 0 CI CH3 CH2C≡C-I 3-F 684 0 0 CI CH 3 CH 2 C≡CI 3-F

685 0 0 CI CH3 CH2C≡C-I 4-F 685 0 0 CI CH 3 CH 2 C≡CI 4-F

686 0 s F H CH2C≡C-I · 一 686 0 s FH CH 2 C≡CI

687 0 s F H CH2C≡C-I 3-F 687 0 s FH CH 2 C≡CI 3-F

688 0 s F H C¾C≡C-I 4-F  6800 0 s F H C¾C≡C-I 4-F

689 0 s F CH3 CH2C≡C-I ― 6890 0 s F CH 3 CH 2 C≡CI ―

690 0 s F CH3 CH2C≡C-I . 3-F 6900 0 s F CH 3 CH 2 C≡CI. 3-F

691 0 s F CH3 CH2C≡C-I 4-F 691 0 s F CH 3 CH 2 C≡CI 4-F

692 0 s CI H CH2C≡C-I 一 692 0 s CI H CH 2 C≡CI 1

693 0 s CI H CH2C≡C-I 3-F 693 0 s CI H CH 2 C≡CI 3-F

694 0 s CI H CH2C≡C-I 4-F 694 0 s CI H CH 2 C≡CI 4-F

695 0 s CI CH3 CH2C≡C-I 一 695 0 s CI CH 3 CH 2 C≡CI 1

696 0 s CI CH3 CH2C≡C-I 3-F 6696 0 s CI CH 3 CH 2 C≡CI 3-F

697 0 s CI CH3 C¾C≡C-I 4-F 经过生物筛选测定， 本发明通式 （I) 的杂环取代的苯并噁嗪环类化合物具有非常 好的生物活性， 部分化合物除草活性优于目前使用的常规除草剂， 在 18.75ga.i/ha的低 剂量施用时， 对大部分阔叶杂草的防效 90%， 对髙粱、 玉米、 水稻、大豆等作物较安 全。 具体实施方式 697 0 s CI CH 3 C¾C≡CI 4-F After biological screening, the heterocyclic substituted benzoxazine ring compounds of the general formula (I) of the present invention have very good biological activity, and the herbicidal activity of some compounds is better than the current one. The conventional herbicide used, when applied at a low dose of 18.75ga.i / ha, has a 90% control effect on most broad-leaved weeds and is safer for crops such as stalks, corn, rice, and soybeans. detailed description

实施例 1 : 制备表中第 120个化合物 N-(7-氟 -3-氧 4-丙炔基 -1,4-苯并噁嗪酮 -6-基) 邻苯二甲酰亚胺 （NO.120)。  Example 1: Preparation of the 120th compound N- (7-fluoro-3-oxo 4-propynyl-1,4-benzoxazinone-6-yl) phthalimide (NO .120).

反应式为：  The reaction formula is:

Figure imgf000021_0001
Figure imgf000021_0001

(NO.120) (NO.120)

取 7-氟 -6-氨基苯并噁嗪酮 1.82g，溶于 20ml冰乙酸中，加入 1.77g邻苯二甲酸酐， 然后加热回流 4小时。冷却， 倾入到 200ml冰水中， 过滤出固体， 水洗， 干燥， 脱溶得 中间体。  Take 1.82 g of 7-fluoro-6-aminobenzoxazinone, dissolve it in 20 ml of glacial acetic acid, add 1.77 g of phthalic anhydride, and heat to reflux for 4 hours. Cool, pour into 200ml ice water, filter out the solid, wash with water, dry, and dissolve to obtain the intermediate.

三口瓶中加入 0.36gNaH， 溶于 150mlDMF中， 搅拌下冷却至 0-5 °C， 慢慢滴加上 述中间体 /50mlDMF， 滴毕， 室温搅拌半小时， 然后室温下慢慢滴加 1.2g溴丙炔， 滴加 完毕， 室温反应 6小时， 倾入冰水中， 用乙酸乙酯萃取， 水洗， 干燥， 柱分得到化合物 (NO.120) 2.66g， 收率 76%。  Add 0.36 g of NaH to a three-necked flask, dissolve it in 150 ml of DMF, cool to 0-5 ° C with stirring, slowly add the above intermediate / 50 ml of DMF dropwise, and after stirring, stir at room temperature for half an hour, then slowly add 1.2 g of bromine at room temperature. After the addition of propyne was completed, the reaction was performed at room temperature for 6 hours, poured into ice water, extracted with ethyl acetate, washed with water, and dried. The column was separated to obtain 2.66 g of the compound (NO.120) with a yield of 76%.

NMR: 4.25(S, 2H) 4.69(d，2H) 6.28(S, 1H) 7.30-7.68(m, 6H) 实施例 2:制备表中第 626个化合物 N-(7-氟 -3-氧 4-碘丙炔基 -1,4-苯并噁嗪酮 -6-基)环己 小烯 -1,2-二羧酰亚胺 （N0.626)。  NMR: 4.25 (S, 2H) 4.69 (d, 2H) 6.28 (S, 1H) 7.30-7.68 (m, 6H) Example 2: Preparation of the 626th compound N- (7-fluoro-3-oxy4) in the table -Iodopropynyl-1,4-benzoxazinone-6-yl) cyclohexene-1,2-dicarboximide (N0.626).

其反应式为：  Its reaction formula is:

Figure imgf000021_0002
Figure imgf000021_0002

(N0.626)  (N0.626)

取 7-氟 -6-氨基苯并噁嗪酮 1.82g， 溶于 20ml冰乙酸中， 加入 1.83g 3， 4, 5， 6- 四氢邻苯二甲酸酐， 然后加热回流 4小时。 冷却， 倾入到 200ml冰水中， 过滤出固体， 水洗， 干燥， 脱溶得中间体。 Take 1.82 g of 7-fluoro-6-aminobenzoxazinone, dissolve it in 20 ml of glacial acetic acid, and add 1.83 g of 3, 4, 5, 6- Tetrahydrophthalic anhydride, then heated to reflux for 4 hours. Cool, pour into 200 ml of ice water, filter out the solid, wash with water, dry, and dissolve to obtain the intermediate.

三口瓶中加入 0.36gNaH， 溶于 150mlDMF中， 搅拌下冷却至 0-5°C， 慢慢滴加上 述中间体 /50mlDMF， 滴毕， 室温搅拌半小时， 然后室温下慢慢滴加 1.2g溴丙炔， 滴加 完毕， 室温反应 6小时，倾入冰水中， 用乙酸乙酯萃取， 7洗，千燥，脱溶得到中间体二。  Add 0.36 g of NaH to a three-necked flask, dissolve it in 150 ml of DMF, cool to 0-5 ° C with stirring, slowly add the above intermediate / 50 ml of DMF dropwise, and stir at room temperature for half an hour, then slowly add 1.2 g of bromine at room temperature After the addition of propyne was completed, the reaction was carried out at room temperature for 6 hours, poured into ice water, extracted with ethyl acetate, washed with 7 hours, dried, and then dissolved to obtain intermediate 2.

上述中间体二溶于 200ml丙酮中， 加入 4.5gN-碘代丁二酰亚胺和 0.2g硝酸银， 室 温搅拌反应 24小时， 柱分得到化合物 （N0.626 ) 2.49g, 收率 52%。  The above intermediate II was dissolved in 200 ml of acetone, 4.5 g of N-iodosuccinimide and 0.2 g of silver nitrate were added, and the reaction was stirred at room temperature for 24 hours. The column was separated to obtain 2.49 g of the compound (N0.626) with a yield of 52%.

NMR: 3.6-3.8(m, 8H) 4.25(S, 2H) 4.72(d, 2H) 7.30(d, 2H)  NMR: 3.6-3.8 (m, 8H) 4.25 (S, 2H) 4.72 (d, 2H) 7.30 (d, 2H)

应用实施例 1 : 盆栽除草试验 Application Example 1: Potted Weed Test

( 1 )试剂  (1) Reagent

准确称取样品， 用适宜的溶剂溶解后， 加少量乳化剂， 再加蒸馏水定容至 10ml采 用适当喷雾机喷洒， 折合单位面积药量为 18. 75ga.i/ha。  Weigh the sample accurately, dissolve it with a suitable solvent, add a small amount of emulsifier, add distilled water to make up to 10ml, and spray with an appropriate sprayer, which is equivalent to 18.75ga.i / ha per unit area.

(2) 试材  (2) Test material

双子叶选用藜 ( Chenopodium album )、 苘麻 ( Abutilon theophrast ) i、 凹头宽 Dicotyledon choose Chenopodium album, Ramie (Abutilon theophrast) i, concave head wide

(Amaranthus ascedense),单子叶选用马唐( Digitaria sanguinalis (Echinochloa crus-galli) 、 狗尾草 ( Setaria iridis)。 (Amaranthus ascedense). Monocots were selected from Digitaria sanguinalis (Echinochloa crus-galli) and Setaria iridis.

( 3 )试材植株的培育  (3) Cultivation of test plants

在截面积 64cm2的塑料盆钵中定量装土， 压平， 浇透水， 选取籽粒饱满、大小一致 的马唐、 稗草、 狗尾草、 苘麻、 藜、 ω头苋种子， 分单、 双子叶植物分钵栽种， 各占钵 面积的 1/3， 覆 lcm厚细土并淋水， 置于温室培养。 待单子叶试材长至 1叶 1心期、 双 子叶试材长至 2片真叶期，用药液进行苗后茎叶喷雾处理，试材播种次日进行苗前土壤 处理。 随后放回温室。 Quantitatively fill the soil in a plastic pot with a cross-sectional area of 64 cm 2 , flatten it, and pour it with water. Select full-grained, uniformly-sized tangs, yarrow, kennel, ramie, quinoa, ω-head cricket seed, single, dicotyledon The plants were planted in separate bowls, each covering one-third of the bowl area, covered with 1 cm thick fine soil and sprinkled with water, and placed in a greenhouse for cultivation. After the monocotyledonous material grows to 1 leaf and 1 heart stage, and the dicotyledonous material grows to 2 true leaf stages, the post-emergence stem and leaf spray treatment is performed with the medicinal solution, and the seedling soil treatment is performed the next day after sowing. It was then returned to the greenhouse.

(4)测试  (4) Test

15后目测地上部生长情况， 计算生长抑制率， 生长抑制率 （％) =100 (对照株高- 处理株高） I对照株高。 根据生长抑制率进行除草活性分级： A级生长抑制率 >90% ； B 级 生长抑制率 75 90% ； C级 生长抑制率 50~75%； D级 生长抑制率 小于 50% 。  After 15 minutes, the above-ground growth condition was visually measured, and the growth inhibition rate was calculated. The growth inhibition rate (%) = 100 (control plant height-treated plant height) I control plant height. According to the growth inhibition rate, the herbicidal activity is graded: A-level growth inhibition rate> 90%; B-level growth inhibition rate 75 90%; C-level growth inhibition rate 50 ~ 75%; D-level growth inhibition rate is less than 50%.

本发明的部分化合物如化合物 N0.69、 120、 137、 626等分别以 18. 75ga.i/ha的施 用量对盆栽试材植株芽后茎叶处理， 抑制毒力效果见表 3。  Some compounds of the present invention, such as compounds N0.69, 120, 137, and 626, were used to treat stem and leaves of potted test plants after buds at an application rate of 18.75ga.i / ha.

表 3: 盆栽除草试验  Table 3: Potted weed test

样品 马唐 稗草 狗尾草 藜 苘麻 凹头苋 Sample tang

N0.69 D D D B B A N0.69 D D D B B A

120 D D D A A A 120 D D D A A A

137 D D D A A A137 D D D A A A

626 D D D A A A 如表 3可知：测试的四个化合物在 18. 75ga.i/ha的低剂量下对阔叶杂草均有很好的 防效,但对禾本科杂草无效。 626 DDDAAA As can be seen from Table 3, the four compounds tested have a good control effect on broad-leaved weeds at a low dose of 18.75ga.i / ha, but have no effect on grass weeds.

应用实施例 2: 作物安全性试验。 Application Example 2: Crop safety test.

选取籽粒饱满、 大小一致的水稻 Oryza sativa、 小麦 Triticum aestivum、 玉 米 Zea mays、高粱 sorghum vulgare、大豆 Glycine max ¾ ¾ Brass ica campestris 种子， 用 0. 1%HgCl2消毒 5 min, 后用蒸馏水浸种 12 h， 滤出放入小瓷盘 （内放润湿 吸水纸）中在 25Ό植物生长箱内催芽 24 h，取大小和芽长一致的种子 10粒，播于 64cm2 定量装土的塑料盆钵中， 覆 1cm厚细土并淋水， 置于温室培养。 待单子叶试材长至 1 叶 1心期、双子叶试材长至 2片真叶期， 用 150、 75、 ' 37.5、 18.75、 9.375、 4.6875ga. i. /ha 药液进行苗后茎叶喷雾处理，试材播种次日进行苗前土壤处理，分别以喷雾溶剂和清水 为对照， 两次重复， 处理试材置于温室培养， 15d后观察作物受害症状， 目测地上部生 长抑制率。 生长抑制率（％) =100 (对照株高-处理株高） I对照株高， 根据生长抑制率 估测作物 IC 值， 并结合杂草 IC9。值， 按 IC' IC9。计算选择性指数（z)， 安全性等 级标准： A : Z > 4 B 2 < Z < 4 C Z < 2 , B级以上可视为安全。 Full-grain and uniform-sized rice Oryza sativa, wheat Triticum aestivum, corn Zea mays, sorghum sorghum vulgare, soybean Glycine max ¾ ¾ Brass ica campestris seeds were sterilized with 0.1% HgCl 2 for 5 min, and then soaked with distilled water for 12 h , Filter out and put it into a small porcelain plate (inside wetting absorbent paper) to promote germination in a 25Ό plant growth box for 24 h, take 10 seeds with the same size and shoot length, and plant it in a plastic pot with a fixed amount of soil of 64 cm 2 Cover with 1cm thick fine soil and sprinkle with water, and place in a greenhouse for cultivation. After monocotyledonous material grows to 1 leaf and 1 heart stage, and dicotyledonous material grows to 2 true leaf stages, 150, 75, '37.5, 18.75, 9.375, 4.6875ga. I. / Ha The leaves were spray-treated, and the pre-emergence soil treatment was performed the next day after sowing the test materials. The spraying solvent and water were used as controls, and the treatment was repeated twice. The treated samples were placed in a greenhouse for cultivation. Observe the symptoms of crop damage 15 days later, and observe the growth inhibition rate above ground. Growth inhibition rate (%) = 100 (control plant height-treated plant height) I control plant height, the crop IC value was estimated based on the growth inhibition rate, and weed IC 9 was combined. Value, press IC 'IC 9 . Calculate selectivity index (z), safety level standard: A: Z> 4 B 2 <Z <4 CZ <2, above B can be regarded as safe.

本发明的化合物（NO. 120)对作物的安全性实验结果见表 4  The safety test results of the compound of the present invention (NO. 120) on crops are shown in Table 4

表 4: 安全性实验  Table 4: Safety experiments

样品 剂量 ga. i/ha 水稻 小麦 油菜 玉米 高梁 大豆  Sample dosage ga.i / ha rice wheat rape corn sorghum soybean

150 C C C C C C 150 C C C C C C

75 C C C C B C75 C C C C B C

NO. 120 37.5 B c c B A B NO. 120 37.5 B c c B A B

18.75 A B c A A A 18.75 A B c A A A

9.375 A B c A A A9.375 A B c A A A

4.6875 A A B A A A 如表 4可见:化合物 NO. 120在 37. 5ga. i/ha的剂量下对高梁安全；在 18. 75ga. i/ha 的较低剂量下对水稻、 玉米和大豆安全。 但对油菜和小麦不安全。 4.6875 A A B A A A As can be seen in Table 4: Compound NO. 120 is safe for sorghum at a dose of 37.5ga.i / ha; it is safe for rice, corn, and soybeans at a lower dose of 18.75ga.i / ha. But it is not safe for rapeseed and wheat.

Claims

权 利 要 求 Rights request 1、 一种具有生物活性的杂环取代苯并噁嗪环类化合物， 其特征在于具有如下结构 通式 （I): 1. A biologically active heterocyclic substituted benzoxazine ring compound, which is characterized by the following structure: General formula (I):
Figure imgf000024_0001
Figure imgf000024_0001
 (Π) (ΠΙ) (Π) (ΠΙ) Y=0， S;  Y = 0, S; W=0, 1；  W = 0, 1; X为 F， CI, CH3, CF3， CN; X is F, CI, CH 3 , CF 3 , CN; R2为 H， C¾， Pli; R 2 is H, C¾, Pli; R为 F， CI, Br, C¾， N02 ; R is F, CI, Br, C¾, N0 2; m表示取代基的数目， 可选 0， 1， 2, 3, 4；  m represents the number of substituents, optionally 0, 1, 2, 3, 4; 当 Het= (II)时， R1为 CH3， CHF2， CH2CH3， CH2CN, CH2CH2CH3, CH2CH=CH2, CH2C≡CH， CH2C≡C-Br, CH2C≡C-C1， CH2C≡C-I, CH2OCH2CH3i When Het = (II), R 1 is CH 3 , CHF 2 , CH 2 CH 3 , CH 2 CN, CH 2 CH 2 CH 3 , CH 2 CH = CH 2 , CH 2 C≡CH, CH 2 C≡ C-Br, CH 2 C≡C-C1, CH 2 C≡CI, CH 2 OCH 2 CH 3i 当 Het= (III)时， R1仅为 CH2C≡C-I。 When Het = (III), R 1 is only CH 2 C≡CI. 2、 根据权利要求 1所述的一种具有生物活性的杂环取代的苯并噁嗪环类化合物， 其特征在于通式（I) 中的 X较好是氟； Y较好是 0; W较好是 1 ; R1较好是炔基、 碘 炔基； R2较好是 H; Rm较好是氢、 氟； 2. A biologically active heterocyclic substituted benzoxazine ring compound according to claim 1, characterized in that X in the general formula (I) is preferably fluorine; Y is preferably 0; W R 1 is preferably alkynyl or iodoalkynyl; R 2 is preferably H ; R m is preferably hydrogen or fluorine; 3、 根据权利要求 1或 2所述的的杂环取代的苯并噁嗪环类化合物的制备方法， 其 特征在于可用如下合成路线得到： 2004/087694 3. The method for preparing a heterocyclic substituted benzoxazine ring compound according to claim 1 or 2, characterized in that it can be obtained by the following synthetic route: 2004/087694
Figure imgf000025_0001
Figure imgf000025_0001
 4、 根据权利要求 1所述的杂环取代苯并噁嗪环类化合物， 其特征在于具有除草活 性，在较低的用量下，对大多数阔叶杂草具有优良的除草活性，并对作物如髙粱、玉米、 水稻、 大豆等较安全。 4. The heterocyclic substituted benzoxazine ring compound according to claim 1, characterized in that it has herbicidal activity, and at a lower amount, it has excellent herbicidal activity against most broad-leaved weeds, and has a good effect on crops Such as sorghum, corn, rice, soybeans, etc. are safer.
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Cited By (6)

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WO2012041789A1 (en) 2010-10-01 2012-04-05 Basf Se Herbicidal benzoxazinones
CN102920709A (en) * 2012-11-15 2013-02-13 山东大学齐鲁医院 Application of 2,3-dihydro-3-hydroxmethyl-6-methyl-[1,4]-benzoxazine in preparation of anti-breast cancer drug
WO2014122674A1 (en) * 2013-02-08 2014-08-14 Rallis India Limited Process for preparation of derivatives of tetrahydrophthalimide
US9101634B2 (en) 2010-05-20 2015-08-11 Shandong University Application of 2, 3-dihydro-3-hydroxymethyl-6-amino-[1,4]-benzoxazine in preparation of drugs inducing embryonic stem cells to differentiate to vascular endothelial cells
US10285923B2 (en) 2011-12-20 2019-05-14 Johnson & Johnson Consumer Inc. Cationic polyglyceryl compositions and compounds
WO2019101513A1 (en) 2017-11-23 2019-05-31 Basf Se Herbicidal pyridylethers

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EP2443102B1 (en) * 2009-06-19 2013-04-17 Basf Se Herbicidal benzoxazinones
EP2794599A1 (en) * 2011-12-23 2014-10-29 Basf Se Process for manufacturing triazinon-benzoxazinones
JP6156074B2 (en) * 2013-11-08 2017-07-05 住友化学株式会社 Succinimide compounds and uses thereof
JP7295088B2 (en) * 2017-07-24 2023-06-20 レダッグ クロップ プロテクション リミテッド Benzoxazinone Derivatives Useful as Herbicides

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9101634B2 (en) 2010-05-20 2015-08-11 Shandong University Application of 2, 3-dihydro-3-hydroxymethyl-6-amino-[1,4]-benzoxazine in preparation of drugs inducing embryonic stem cells to differentiate to vascular endothelial cells
WO2012041789A1 (en) 2010-10-01 2012-04-05 Basf Se Herbicidal benzoxazinones
US10285923B2 (en) 2011-12-20 2019-05-14 Johnson & Johnson Consumer Inc. Cationic polyglyceryl compositions and compounds
CN102920709A (en) * 2012-11-15 2013-02-13 山东大学齐鲁医院 Application of 2,3-dihydro-3-hydroxmethyl-6-methyl-[1,4]-benzoxazine in preparation of anti-breast cancer drug
WO2014122674A1 (en) * 2013-02-08 2014-08-14 Rallis India Limited Process for preparation of derivatives of tetrahydrophthalimide
WO2019101513A1 (en) 2017-11-23 2019-05-31 Basf Se Herbicidal pyridylethers

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