CN1194975C - 一种具有生物活性的杂环取代苯并噁嗪环类化合物 - Google Patents
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- C—CHEMISTRY; METALLURGY
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- 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
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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
-
- 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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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract
本发明公开了通式(I)所示的杂环取代的苯并噁嗪环类化合物及其制备方法。其中式(1)Het为：Y＝O，S；W＝0，1；X为F，Cl，CH3，CF3，CN；R2为H，CH3，Ph；R为F，Cl，Br，CH3，NO2；m表示取代基的数目，可选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-Cl，CH2C≡C-I，CH2OCH2CH3，当Het＝(III)时，R1仅为CH2C≡C-I。本发明化合物具有优异的除草活性，在18.75ga.i/ha的低剂量施用时，部分化合物对大多数阔叶杂草的防效≥90%，对高粱、玉米、水稻、大豆等作物较安全。
Description
技术领域：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：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、US4640707、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。
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性。
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，芽后茎叶处理会对作物本身造成伤害，只适用于作物的芽前土壤处理，对生长期内杂草防效较差。
发明内容：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，更重要的特点是适用于芽后处理，对水稻、高梁、大豆、玉米等作物安全。本发明的结构通式(I)如下：
式(1)中Het为：
Y＝O，S；较好是O；
W＝0，1；较好是1；
X为F，Cl，CH3，CF3，CN；较好是氟；
R2为H，CH3，Ph；较好是H；
R为F，Cl，Br，CH3，NO2；较好是氟；
m表示取代基的数目可选0，1，2，3，4；较好是0；
当Het＝(II)时，R1为CH3，CHF2，CH2CH3，CH2CN，CH2CH2CH3，CH2CH＝CH2，CH2C≡CH，CH2C≡C-Br，CH2C≡C-Cl，CH2C≡C-I，CH2OCH2CH3；较好是丙炔基、碘丙炔基；
当Het＝(III)时，R1仅为CH2C≡C-I；
本发明中通式(I)化合物的制备方法如下：
式中W，X，Y，R，R1，R2，m同权利要求1所定义；
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30～150℃，搅拌反应1～12小时得到(C)。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。
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＝1∶1∶1.2；较佳的温度25℃；较优的反应时间8小时。
中间体(A)的合成参考文献US4734124方法如下：
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℃，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K2CO3；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。
化合物(E)加入到含还原铁粉的适当溶剂中，加热至30℃～120℃，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80℃；较优的反应时间为3小时。
化合物(F)加入到80％硫酸中，冷却到0℃，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。
(见表1) (见表2)
表1：
| NO | W | Y | X | R2 | R1 | Rm |
| 123456789101112131415161718192021222324252627282930313233343536373839404142 | 111111111111111111111111111111111111111111 | OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO | FFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF | HHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH | CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CN | 3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl |
| NO | W | Y | X | R2 | R1 | Rm |
| 434445464748495051525354555657585960616263646566676869707172737475767778798081828384 | 111111111111111111111111111111111111111111 | OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO | FFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF | HHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH | CH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3 | 4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F |
| NO | W | Y | X | R2 | R1 | Rm |
| 858687888990919293949596979899100101102103104105106107108109110111112113114115116117118119120121122123124125126 | 111111111111111111111111111111111111111111 | OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO | FFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF | HHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH | CH2CH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CH | 3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F |
| NO | W | Y | X | R2 | R1 | RM |
| 127128129130131132133134135136137138139140141142143144145146147148149150151152153154155156157158159160161162163164165166167168 | 111111111111111111111111111111111111111111 | OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO | FFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF | HHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH | CH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-Cl | 4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl |
| 169170171172173174175176177178179180181182183184185186187188189190191192193194195196197198199200201202203204205206207208209210 | 111111111111111111111111111111111111111111 | OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO | FFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF | HHHHHHHHHHHHHHHHHHHCH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3 | CH2C≡C-ClCH2C≡C-ClCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CHF2CHF2CHF2CHF2CHF2CHF2 | 3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO2 |
| NO | W | Y | X | R2 | R1 | Rm |
| 212212213214215216217218219220221222223224225226227228229230231232233234235236237238239240241242243244245246247248249250251252 | 111111111111111111111111111111111111111111 | OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO | FFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF | CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3 | CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CNCH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3CH2CH3 | 4-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl |
| NO | W | Y | X | R2 | R1 | Rm |
| 253254255256257258259260261262263264265266267268269270271272273274275276277278279280281282283284285286287288289290291292293294 | 111111111111111111111111111111111111111111 | OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO | FFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF | CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3 | CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2OCH2CH3CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2 | 3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH3 |
| NO | W | Y | X | R2 | R1 | Rm |
| 295296297298299300301302303304305306307308309400401402403404405406407408409410411412413414415416417418419420421422423424425426 | 111111111111111111111111111111111111111111 | OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO | FFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF | CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3 | CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2CH＝CH2CH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-I | 3-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F |
| NO | W | Y | X | R2 | R1 | Rm |
| 427428429430431432433434435436437438439440441442443444445446447448449450451452453454455456457458459460461462463464465466467468 | 111111111111111111111111111111111111111111 | OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO | FFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF | CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3PhPhPhPh | CH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-ClCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2C≡C-BrCH2CH2CH3CH2C≡CHCH2OCH2CH3CH2C≡C-I | 4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br-3-Cl3-Br3-F3-CH33-NO24-F4-Cl4-Br4-CH34-NO23，6-2Cl3，6-2F4，5-2Cl3，4，5，6，-4Cl3，4，5，6，-4F3，4，5，6，-4Br---- |
| NO | W | Y | X | R2 | R1 | Rm |
| 469470471472473474475476477478479480481482483484485486487488489490491492493494495496497498499500501502503504505506507508509510 | 111111111111111111111111111111111111111111 | OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO | ClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClCl | HHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH | CH3CHF2CH2CNCH2CH3CH2CH2CH3CH2OCH2CH3CH2CH＝CH2CH2C≡CHCH2C≡C-ICH2C≡C-ClCH2C≡C-BrCH3CHF2CH2CNCH2CH3CH2CH2CH3CH2OCH2CH3CH2CH＝CH2CH2C≡CHCH2C≡C-ICH2C≡C-ClCH2C≡C-BrCH3CHF2CH2CNCH2CH3CH2CH2CH3CH2OCH2CH3CH2CH＝CH2CH2C≡CHCH2C≡C-ICH2C≡C-ClCH2C≡C-BrCH3CHF2CH2CNCH2CH3CH2CH2CH3CH2OCH2CH3CH2CH＝CH2CH2C≡CHCH2C≡C-I | -----------3-F3-F3-F3-F3-F3-F3-F3-F3-F3-F3-F4-F4-F4-F4-F4-F4-F4-F4-F4-F4-F4-F3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F |
| NO | W | Y | X | R2 | R1 | Rm |
| 511512513514515516517518519520521522523524525526527528529530531532533534535536537538539540541542543544545546547548549550551552 | 111111111111111111111111111111111111111111 | OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO | ClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClClCl | HHCH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3 | CH2C≡C-ClCH2C≡C-BrCH3CHF2CH2CNCH2CH3CH2CH2CH3CH2OCH2CH3CH2CH＝CH2CH2C≡CHCH2C≡C-ICH2C≡C-ClCH2C≡C-BrCH3CHF2CH2CNCH2CH3CH2CH2CH3CH2OCH2CH3CH2CH＝CH2CH2C≡CHCH2C≡C-ICH2C≡C-ClCH2C≡C-BrCH3CHF2CH2CNCH2CH3CH2CH2CH3CH2OCH2CH3CH2CH＝CH2CH2C≡CHCH2C≡C-ICH2C≡C-ClCH2C≡C-BrCH3CHF2CH2CNCH2CH3CH2CH2CH3CH2OCH2CH3CH2CH＝CH2 | 3，4，5，6，-4F3，4，5，6，-4F-----------3-F3-F3-F3-F3-F3-F3-F3-F3-F3-F3-F4-F4-F4-F4-F4-F4-F4-F4-F4-F4-F4-F3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F |
| NO | W | Y | X | R2 | R1 | Rm |
| 553554555556557558559560561562563564565566567568569570571572573574575576577578579580581582583584585586587588589590591592593594 | 111111111111111111111111110000000000000000 | OOOOSSSSSSSSSSSSSSSSSSSSSSOOOOOOOOOOOOOOOO | ClClClClFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF | CH3CH3CH3CH3HHHHHHHHHHHCH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3HHHHHHHHHHHCH3CH3CH3CH3CH3 | CH2C≡CHCH2C≡C-ICH2C≡C-ClCH2C≡C-BrCH3CHF2CH2CNCH2CH3CH2CH2CH3CH2OCH2CH3CH2CH＝CH2CH2C≡CHCH2C≡C-ICH2C≡C-ClCH2C≡C-BrCH3CHF2CH2CNCH2CH3CH2CH2CH3CH2OCH2CH3CH2CH＝CH2CH2C≡CHCH2C≡C-ICH2C≡C-ClCH2C≡C-BrCH3CHF2CH2CNCH2CH3CH2CH2CH3CH2OCH2CH3CH2CH＝CH2CH2C≡CHCH2C≡C-ICH2C≡C-ClCH2C≡C-BrCH3CHF2CH2CNCH2CH3CH2CH2CH3 | 3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F3，4，5，6，-4F-------------------------------------- |
| NO | W | Y | X | R2 | R1 | Rm |
| 595596597598599600601602603604605606607608609610611612613614615616617618619620621622623624625 | 0000000000000000000000000000111 | OOOOOOSSSSSSSSSSSSSSSSSSSSSSOOO | FFFFFFFFFFFFFFFFFFFFFFFFFFFFCH3CF3CN | CH3CH3CH3CH3CH3CH3HHHHHHHHHHHCH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3HHH | CH2OCH2CH3CH2CH＝CH2CH2C≡CHCH2C≡C-ICH2C≡C-ClCH2C≡C-BrCH3CHF2CH2CNCH2CH3CH2CH2CH3CH2OCH2CH3CH2CH＝CH2CH2C≡CHCH2C≡C-ICH2C≡C-ClCH2C≡C-BrCH3CHF2CH2CNCH2CH3CH2CH2CH3CH2OCH2CH3CH2CH＝CH2CH2C≡CHCH2C≡C-ICH2C≡C-ClCH2C≡C-BrCH2C≡CHCH2C≡CHCH2C≡CH | ------------------------------- |
表2：
| NO | W | Y | X | R2 | R1 | Rm |
| 626627628629630631632633634635636637638639640641642643644645646647648649650651652653654655656657658659660661662663664665666667 | 111111111111111111111111111111111111000000 | OOOOOOOOOOOOOOOOOOOOOOOOSSSSSSSSSSSSOOOOOO | FFFFFFClClClClClClFFFFFFClClClClClClFFFFFFClClClClClClFFFFFF | HHHCH3CH3CH3HHHCH3CH3CH3HHHCH3CH3CH3HHHCH3CH3CH3HHHCH3CH3CH3HHHCH3CH3CH3HHHCH3CH3CH3 | CH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-I | -3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F |
| NO | W | Y | X | R2 | R1 | Rm |
| 668669670671672673674675676677678679680681682683684685686687688689690691692693694695696697 | 000000000000000000000000000000 | OOOOOOOOOOOOOOOOOOSSSSSSSSSSSS | ClClClClClClFFFFFFClClClClClClFFFFFFClClClClClCl | HHHCH3CH3CH3HHHCH3CH3CH3HHHCH3CH3CH3HHHCH3CH3CH3HHHCH3CH3CH3 | CH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-ICH2C≡C-I | -3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-F-3-F4-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％。并且芽后茎叶处理对高粱、玉米、水稻、大豆等作物安全。
具体实施方式：
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)。
反应式为：
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。
三口瓶中加入0.36gNaH，溶于150mlDMF中，搅拌下冷却至0-5℃，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％。
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-1-烯-1，2-二羧酰亚胺(NO.626)。
其反应式为：
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。
三口瓶中加入0.36gNaH，溶于150mlDMF中，搅拌下冷却至0-5℃，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，脱溶得到中间体二。
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(NO.626)2.49g，收率52％。
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
(1)试剂
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。
(2)试材
双子叶选用藜(Chenopodium album)、茴麻(Abutilon theophrast)i、凹头苋(Amaranthus ascedense)，单子叶选用马唐(Digitaria sanguinalis)、稗草(Echinochloacrus-galli)、狗尾草(Setaria viridis)。
(3)试材植株的培育
在截面积64cm2的塑料盆钵中定量装上，压平，浇透水，选取籽粒饱满、大小一致的马唐、稗草、狗尾草、茴麻、藜、凹头苋种子，分单、双子叶植物分钵栽种，各占钵面积的1/3，覆1cm厚细上并淋水，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。
(4)测试
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)/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％。
本发明的部分化合物如化合物NO.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。
表3：盆栽除草试验
样品 马唐 稗草 狗尾草 藜 茴麻 凹头苋
NO.69 D D D B B A
120 D D D A A A
137 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。
应用实施例2：作物安全性试验。
选取籽料饱满、大小一致的水稻Oryza sativa、小麦Triticum aestivum、玉米Zeamays、高粱sorghum vulgare、大豆Glvcine max和油菜Brassica campestris种子，用0.1％HgCl2消毒5min，后用蒸馅水浸种12h，滤出放入小瓷盘(内放润湿吸水纸)中在25℃植物生长箱内催芽24h，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)/对照株高，根据生长抑制率估测作物IC’10值，并结合杂草IC90值，按IC’10/IC90计算选择性指数(Z)，安全性等级标准：A∶Z＞4B 2＜Z＜4 C Z＜2，B级以上可视为安全。
本发明的化合物(NO.120)对作物的安全性实验结果见表4
表4：安全性实验
剂量ga.i/ha 水稻 小麦 油菜 玉米 高粱 大豆
样品
150 C C C C C C
75 C C C C B C
NO.120 37.5 B C C B A B
18.75 A B C A A A
9.375 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。
Claims (4)
1一种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)：
其中式(I)Het为：
Y＝O，S；
W＝0，1；
X为F，Cl，CH3，CF3，CN；
R2为H，CH3，Ph；
R为F，Cl，Br，CH3，NO2；
m表示取代基的数目可选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-Cl，CH2C≡C-I，
CH2OCH2CH3；
当Het＝(III)时，R1仅为CH2C≡C-I；
2根据权利要求1所述的一种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是氟；Y是O；W是1；R1是丙炔基、碘丙炔基；R2是H；m＝0或R是氟；
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；
式中W，X，Y，R，R1，R2，m同权利要求1所定义；
4根据权利要求1和2所述的杂环取代苯并噁嗪环类化合物的用途，其特征在于具有除草活性，在低剂量下，对阔叶杂草具有优良的除草活性，并对高粱、玉米、水稻、大豆作物安全。
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| AU2003304029A AU2003304029A1 (en) | 2003-03-31 | 2003-06-27 | A heterocycle-substituted benzoxazine compounds having bioactivity |
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| US8986665B2 (en) | 2007-06-29 | 2015-03-24 | Johnson & Johnson Consumer Companies, Inc. | Cationic polyglyceryl compositions and compounds |
| CN102459205B (zh) * | 2009-06-19 | 2014-11-12 | 巴斯夫欧洲公司 | 除草的苯并*嗪酮类 |
| CN101836993B (zh) | 2010-05-20 | 2011-06-22 | 山东大学 | 2，3-二氢-3-羟甲基-6-氨基-[1，4]-苯并噁嗪在制备诱导胚胎干细胞向血管内皮细胞分化药物中的应用 |
| JP2013540113A (ja) | 2010-10-01 | 2013-10-31 | ビーエーエスエフ ソシエタス・ヨーロピア | 除草性ベンゾオキサジノン |
| EP2794599A1 (en) * | 2011-12-23 | 2014-10-29 | Basf Se | Process for manufacturing triazinon-benzoxazinones |
| CN102920709B (zh) * | 2012-11-15 | 2014-01-08 | 山东大学齐鲁医院 | 2,3-二氢-3-羟甲基-6-甲基-[1,4]-苯并噁嗪在制备抗乳腺癌药物中的应用 |
| WO2014122674A1 (en) * | 2013-02-08 | 2014-08-14 | Rallis India Limited | Process for preparation of derivatives of tetrahydrophthalimide |
| JP6156074B2 (ja) * | 2013-11-08 | 2017-07-05 | 住友化学株式会社 | スクシンイミド化合物及びその用途 |
| WO2019020987A1 (en) * | 2017-07-24 | 2019-01-31 | Redag Crop Protection Ltd. | BENZOXAZINONE DERIVATIVES USEFUL AS HERBICIDES |
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