CN87103167A - 二苯醚衍生物 - Google Patents
二苯醚衍生物 Download PDFInfo
- Publication number
- CN87103167A CN87103167A CN87103167.1A CN87103167A CN87103167A CN 87103167 A CN87103167 A CN 87103167A CN 87103167 A CN87103167 A CN 87103167A CN 87103167 A CN87103167 A CN 87103167A
- Authority
- CN
- China
- Prior art keywords
- formula
- diphenyl ether
- ether derivative
- represent
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 125000005843 halogen group Chemical group 0.000 claims abstract description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 33
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- -1 alkali metal salt Chemical class 0.000 claims description 11
- 230000002363 herbicidal effect Effects 0.000 claims description 9
- 241000196324 Embryophyta Species 0.000 claims description 6
- 150000001340 alkali metals Chemical group 0.000 claims description 6
- 125000002521 alkyl halide group Chemical group 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 241001597008 Nomeidae Species 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 125000001188 haloalkyl group Chemical group 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 16
- 239000002689 soil Substances 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
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- 239000007787 solid Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
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- 240000007594 Oryza sativa Species 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- 238000001816 cooling Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
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- 239000004563 wettable powder Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 230000008635 plant growth Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000002769 thiazolinyl group Chemical group 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
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- 235000007319 Avena orientalis Nutrition 0.000 description 2
- 241000335053 Beta vulgaris Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 102100038736 Histone H3.3C Human genes 0.000 description 2
- 101001031505 Homo sapiens Histone H3.3C Proteins 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical class [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
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- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000011091 sodium acetates Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- NGDBDQFXNPAFJD-UHFFFAOYSA-N 3h-2-benzofuran-1-one;phenoxybenzene Chemical compound C1=CC=C2C(=O)OCC2=C1.C=1C=CC=CC=1OC1=CC=CC=C1 NGDBDQFXNPAFJD-UHFFFAOYSA-N 0.000 description 1
- 235000007558 Avena sp Nutrition 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 235000021533 Beta vulgaris Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- NBJIBSAUQOMIRS-UHFFFAOYSA-N O.C(CCC)[K] Chemical group O.C(CCC)[K] NBJIBSAUQOMIRS-UHFFFAOYSA-N 0.000 description 1
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- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
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- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
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Abstract
具有通式I的二苯醚衍生物
式中R1代表一个氢原子或卤原子,或一个烷基或卤烷基;R2和R3可以是相同的或不同的,它们分别代表一个氢原子或卤原子或一个烷基、卤烷基、硝基或氰基;R4代表一个氢原子或一个烷基。
Description
本发明涉及二苯醚衍生物,其制备方法含有本衍生物的除草剂组合物及其控制不需要的植物生长的应用。
在欧洲专利No.145,078中,已知通式Ⅰ的二苯醚衍生物具有除草的活性。
式中R1代表一个氢或者卤原子,或者一个烷基或卤烷基;
现在出人意外地发现:当通式Ⅰ的二苯醚衍生物中的A基团代表某些烯基时,显示出有趣的除草剂的活性,其除草的水平是其他类似结构式的化合物无法比拟的。
当本发明的化合物含有一个烷基时,烷基可以是直链的或支链的,可以含有10个碳原子,较好的是6个,最好是4个碳原子,合适的例子是甲基、乙基和丙基。
较好的化合物是R1代表一个卤烷基,特别是三氟甲基,R2代表一个卤原子,特别是氯原子,R3代表氢。
在某些发明的具体实例中,R4代表烷基,较好的是C1-4的烷基,例如甲基或乙基。
在其他一些发明实例中,R4代表氢原子。
本发明更进一步地提供了一种制备上述二苯醚衍生物的方法,包括通式Ⅱ的苯酞
与通式Ⅲ的化合物的反应。
式中R1、R2和R3所代表的基团与通式Ⅰ的含义相同,Q和W的一种形式是代表卤原子或硝基,另一种形式是代表分子式-OM的基团,其中M代表氢原子或碱金属原子。反应最好是将式Ⅱ的化合物(其中Q是羟基)与碱金属氢氧化物或氢化物反应,在一种适宜的溶剂中反应,形成一种碱金属盐,再将此碱金属盐与式Ⅲ的化合物(其中W代表一个氯原子)反应。碱金属氢氧化物与式Ⅱ的化合物的反应适于在链烷醇溶剂如:乙醇中进行,后一个反应,即碱金属氢化物与式Ⅲ的化合物的反应以及碱金属盐与氯代化合物的反应最好在适宜的质子惰性有机溶剂,如二甲基亚砜,环丁砜,二甲基替甲酰胺,或二甲替乙酰胺中反应。后一个反应适于在升温下,如25℃以上,特别是40℃和迥流温度之间进行,反应适于在迥流下并有惰性气体如:氮的存在下进行。
另一种制备式Ⅰ化合物的方法是将式Ⅳ的化合物。
与通式为(R4)H2C-L的化合物反应,式中L是适宜的离去基团,它包括羧基以及它们的烷基酯,碱金属衍生物。反应适于在升温下进行,较好的温度是150-400℃之间。化合物中 C=C(R4)(H)代表 C=CH2,此化合物可以用具有CH-CH2-OH取代基的前身化合物进行脱水来制备,因此如要获得通式Ⅴ的化合物,
可用通式Ⅵ的化合物进行脱水,
脱水步骤适于在升温下(例如:从50℃到迥流的温度)及羧酸酐((例如:醋酸酐)存在下进行。制备通式Ⅵ化合物的方法是将相应的甲基取代衍生物进行卤化(如:溴化),再对生成的卤甲基进行水合反应。一些情况下,上述反应在适宜的溶剂中进行,另一些情况下,加入过量的反应物之一以形成一种适宜的反应溶剂。
后一个步骤,反应条件也要适宜,例如上述的水含作用(在水中进行),脱水作用(在羧酸酐中进行)。
制备通式Ⅰ的化合物的另一方法是将通式Ⅶ的苯酞
式中R1,R2和R3所代表的基团与上述通式Ⅰ的含义相同与下式的乙缩醛化合物进行反应,
式中每一个R5分别代表烷基,最好含有1-4个碳原子。此反应适于在升温下,如从40℃到反应混合物的迥流温度,并在氮的存在下进行。最好还有催化剂,适合的催化剂包括碱金属醇盐,如特一丁醇钾。
所述的起始材料是已知的或者可用常规方法通过已知的化合物来制备的。例如通式Ⅲ,Ⅵ(以及其甲基前身和EP-A-145078中所公开的通式Ⅶ的化合物。通式Ⅳ化合物是已知的(见化学摘要73(19)卷,986642号)而用刚才已述的类似方法对化合物的苯酞部分进行变化就可制备通式Ⅱ的化合物,它们用于制备二苯醚苯酞。
现在发现具有通式Ⅰ的化合物可显示出有趣的除草剂的活性。因此发明进一步地提供了一种除草剂组合物,组合物包含上述的通式Ⅰ的化合物以及至少一种载体,并提供了制备此组合物的方法,包括将通式Ⅰ的化合物与至少一种载体相混合。据发现本发明的化合物具有出人意外的高水平的除草剂的活性,特别是与含有类似烯基的其他化合物相比较时活性水平尤高。
本发明还提供了此化合物或组合物作为除草剂的应用方法。本发明进而提供了一种用化合物或组合物处理植物生长的场所以控制不需要的植物生长的方法。
施用本除草剂处理的场所可以是芽前或芽后,应用活性成分的剂量是0.05-10公斤/公顷,最好是0.1-4公斤/公顷。
本发明中组合物的载体可以是任何一种材料,这些材料可与活性成分一起形成一种便于应用到各种场所(如:植物、种子、土壤)或便于贮藏或运输或搬运的剂型。载体可以是固体的或液体的,包括一种材料在常态时是气体,但可以压缩成液体保存,使用任何一种使除草剂组合物形成剂型的载体。较好的组合物含有重量0.5-90%的活性成分。
适宜的固体载体有天然的和合成的粘土及硅酸盐,例如天然硅石,如硅藻土;硅酸镁,如滑石;硅酸铝镁如活性白土和蛭石,硅酸铝,如高岭土,蒙脱土和云母;碳酸钙,硫酸钙;硫酸铵;合成水合氧化硅和合成硅酸钙或硅酸铝;元素如碳和硫;天然的和合成的树脂,如苯并呋喃树脂聚氯乙烯、苯乙烯聚合物和共聚物;固体多氯酚;沥青;蜡;以及固体肥料,如过磷酸钙。
适宜的液体载体,包括水;醇,如异丙醇和乙二醇;酮,如丙酮、甲基乙基酮、甲基异丁基酮和环己酮;醚;芳香族或脂肪族烃,如苯甲苯和二甲苯;石油馏分,如煤油和轻矿物油;氯化烃,如四氯化碳,全氯乙烯和三氯乙烷。
较适宜的是不同液体的混合物。
农业上的组合物常以浓缩物的形式存在,便于运输,而用前使用者再将之稀释。组合物内有少量表面活性剂载体,有利于稀释。最好本发明的组合物中至少有一种载体是表面活性剂。如组合物可以含有至少两种载体。而其中至少有一种载体是表面活性剂。
表面活性剂可以是乳化剂,分散剂或润湿剂;可以是非离子型也可以是离子型的。较适宜的表面活性剂如聚丙烯酸的钠盐或钙盐以及木质磺酸;分子中含有至少12个碳原子的脂肪酸或脂肪胺或脂肪酰胺与氧化乙烯和/或氧化丙烯缩合的产物;甘油山梨糖醇酐、蔗糖或季戍四醇的脂肪酸酯;这些化合物与氧化乙烯和/或氧化丙烯缩合的产物;脂肪醇或烷基苯酚,如对-辛酚或对-辛甲酚与氧化乙烯和/或氧化丙烯的缩合产物;以及这些与硫酸或磺酸盐的缩合产物;碱或碱土金属盐,较好的是分子中含有至少10个碳原子的硫酸酯或磺酸酯的钠盐,如十二烷基硫酸钠,另烷基-烷基硫酸钠,磺酸蓖麻油钠盐,(烷基芳基、磺酸钠,如十二烷基苯磺酸钠;氧化乙烯聚合物和氧化乙烯和氧化丙烯共聚物。
本发明的组合物可以制成可湿性粉剂、粉剂、粒剂、溶液,乳油、乳剂,混悬浓缩物,以及烟雾剂。
可湿性粉剂通常含有重量的25%、50%或75%的活性成份并含有附加的固体惰性载体,重量的3-10%的分散剂,必要时,含有重量的0-10%的稳定剂和/或其他附加剂如渗透剂或粘胶剂。粉剂通常制成类似于可湿性粉剂的粉剂,但没有分散剂,并进一步用固体载体稀释以制成含有重量的1/2-10%的活性成份的组合物。通常制成的颗粒剂的规格可通过10-100BS的筛网(1.676-0.152毫米),用附聚作用或浸透方法制备。一般说来,颗粒剂含有重量1/2-75%的活性成份和重量的0-10%的附加成份,例如稳定剂,表面活化剂,缓释剂和粘合剂。这种称作“干燥的流动性粉剂”由含有相当高浓度的活性成份的小颗粒所组成。乳油除了含有溶剂或必要时含有复合溶剂外,还含有10-50%重量/体积的活性成份,2-20%重量/体积的乳化剂以及0-20%重量/体程的其他成份如稳定剂、渗透剂和防腐剂。混悬浓缩液通常是用混合的方法制备成一种稳定且不沉淀的流动药剂,一般含有10-75%重量比的活性成份;0.5%-15%重量比的分散剂,0.1%-10%重量比的混悬剂,如保护性胶体和触变剂,0-10%重量比的其他附加成份,如去末剂、防腐剂、稳定剂、渗透剂和粘胶剂,水或者活性成份实际上不溶于其中的有机液体;还可以含有某些有机固体或无机盐,溶于药剂中有助于防止沉淀或者做为水的抗冻剂。
用水将本发明中的可湿性粉剂或浓缩物稀释,制成含水分散剂和乳剂,均在本发明的范围之内。所说乳剂可以是油包水型或水包油型,其稠度类似于“蛋黄酱”。
本发明的组合物也可以含有其他成份,如其他具有除草剂、杀虫剂、杀菌剂特性的化合物。
下列例1和例2有关本发明的使用,而例3-例8所描述的化合物是在发明范围之外。
例1.5-(2-氯-4-三氟甲基苯氧基)-3-亚甲-1-(3H)异苯并呋喃酮(1)的制备
将3.4克5-(2-氯-4-三氟甲基苯氧基)-3-甲基苯酞溶于50毫升四氯化碳中,加入2.0克的N-溴代丁二酰亚胺以及一片过氧化苯酰作催化剂将混合物在明亮的光线下迥流1 1/2 小时。然后冷却混合物,滤去溶剂,在滤渣中加入50毫升水,迥流3小时。再滤去水,滤渣用干燥甲苯脱水,用共沸蒸馏法除去甲苯/水获得一个干燥固体。将50毫升醋酸酐加到固体中,迥流过夜。滤去溶剂,在滤渣中加入饱和的碳酸氢盐溶液。用二氯甲烷萃取水相,再用水洗有机层,干燥。滤去有机溶剂,滤渣在二氧化硅上进行色层分离纯化,用二氯甲烷作淋洗液。获得2.0克的(1),熔点92-94℃
分析:计算值:C56.4;H2.4%
实验值:C55.8;H2.6%
例2和例3
5-和6-(2-氯-4-三氟甲基-苯氧基)-3-甲基亚甲基-1-(3H)异苯并呋喃酮(2和3)的制备
将34.25克的5-(2-氯-4-三氟甲基苯氧基)酞酐和9.6克的丙酸钠溶于100毫升丙酸酐中,搅拌并在170℃油浴中加热4小时。在旋转蒸发器上蒸去大部分酸酐,用甲苯和水处理固体滤渣。分离有机层,用软水洗,并蒸发至干。残留的油等分成两份。将一份在硅胶上色层分离,用二氯甲烷作洗脱液,得4.35克的(2)和1.25克的(3)
从甲苯中重结晶。例2熔点121-123℃;例3:熔点144-145.4℃。
分析:计算值:C57.5;H2.8%
实验值:C57.5;H2.8%
实验值:C57.3;H2.9%
例4和5
6-和5-(2-氯-4-三氟甲基苯氧基)-3-(2-甲氧基苯基亚甲基)-1-(3H)异苯并呋喃酮(4和5)的制备。
将6.8克的5-(2-氯-4-三氟甲基苯氧基)-酞酐,3.65克的0-甲氧基苯基乙酸和4.9克的醋酸钠混合在一起,在油浴上加热230℃-240℃2小时,反应物冷却并用沸乙醇萃取。过滤热乙醇溶液并冷却产生黄色沉淀。收集沉淀并溶解在二氯甲烷中。将溶液进行高压液相色谱纯化,用20%的四氢呋喃溶于己烷的溶液作淋洗液,得1.15克的(4),熔点152℃,得1.35克的(5),熔点147℃。
分析 计算值:C61.8;H3.1%
实验值(4):C62.0;H3.5%
实验值(5):C61.1;H3.2%
例6和例7
6-和5-(2-氯-4-三氟甲基苯氧基)3-苯基亚甲基-1-(3H)异苯并呋喃酮(6和7)的制备
制备方法与例4和例5相似,将6.8克的5-(2-氯-4-三氟甲基苯氧基)酞酐,4.9克醋酸钠和3.0克的苯基乙酸混合后在230℃-240℃下加热。反应混合物再按例4和例5中所述方法进行处理,得1.4克的(6),熔点139-140℃,得2.8克的(7),熔点147-148℃。
分析:计算值:C63.4;H2.9%
实验值(6):C62.9;H2.9%
实验值(7):C63.1;H2.9%
例8
5-(2-氯-4-三氟甲基苯氧基)-3-二甲基氨基亚甲基-1-(3H)-异苯并呋喃酮,Z-异构体。
将3.3克的5-(2-氯-4-三氟甲基苯氧基)苯酞和溶于5毫升的二甲基甲酰胺二甲基乙缩醛的一定量的催化剂特丁基氧化钾相混合,在氮气下进行迥流。1小时和3小时之后,将5毫升乙缩醛加入到混合物中。再迥流1小时之后,混合物冷却,折出结晶。混合物分成两相,水/二氯甲烷系统,干燥有机层,除去溶剂,将残渣在二氧化硅上色层分离纯化,用二氯甲烷作淋洗剂,产生标题化合物,熔点145-147℃。
分析 计算值:C56.3;H3.4;N3.65%
实验值:C56.1;H3.5;N3.0%
除草剂活性
为了评价所制备的化合物的除草剂活性,使用下列植物作代表进行试验:玉米(Zen mays)(M2);水稻,Oryza sativa(R);稗草,Echinochloc crusgalli(BG);燕麦,Avena sativa(O);亚麻,Linum usitatissimun(L);芥子,Sinapsis alba(M);甜菜;Beta vulgaris(SB)以及大豆,Glycine max(S)。
将试验分成两种类型,芽前和芽后。芽前试验是将化合物液体加工剂型喷施于土壤中,土壤里已经播种了上述植物的种子。芽后试验有两种类型,即:土壤浸润和叶面喷施的试验。土壤浸润试验是用本发明的化合物配制的液体浸润土壤,上述植物的秧苗正在此土壤中生长,叶面喷施试验是用此配制的液体喷洒在植物秧苗上。
试验中所用土壤是制备好的园艺肥土。
试验所用的配方液体是将试验的化合物溶于丙酮,丙酮中含有0.4%重量比的烷基苯酚/氧化乙烯缩合物,商标名如TRITONX-155。用水稀释丙酮溶液,在土壤喷洒和叶面喷施试验中喷洒的液体剂量相当于每公顷喷洒5公斤或1公斤的活性成份,其体积相当于每公顷喷洒600升,而在土壤浸润试验中,喷洒的液体剂量相当于每公顷喷洒600升,而在土壤浸润试验中,喷洒的液体剂量相当于每公顷喷洒10公斤的活性成分,其体积相当于每公顷约喷洒3000升。
在芽前试验中,未经处理的已播种的土壤和在芽后试验中,生长着未经处理的植物秧苗的土壤都作为对照组。
喷洒叶面和土壤12天之后,浸润土壤13之后用视觉评价试验化合物的除草剂效果,并用0-9的尺度记录结果,级别O表示如同未经处理的对照物一样地生长,级别9表示死亡。在线形标尺上每增加1个单位约等于效果增加10%。
试验结果列于下表,表中化合物的号数与前面例子中所提及的化合物号数一致。
Claims (16)
2、根据权项1的二苯醚衍生物,其中R1代表一个卤烷基,R2代表一个卤原子,R3代表氢原子。
3、根据权利1或2的二苯醚衍生物,其中R4代表一个氢原子或C1-4的烷基。
4、根据权项1的二苯醚衍生物,如上面所述或实质上特别是例1和例2所述衍生物。
6、根据权项5的方法,其中通式Ⅱ的苯酞的Q为羟基与氢氧化碱金属或氢化碱金属反应形成碱金属盐,碱金属盐与通式Ⅲ的化合物反应,其中W代表一个氯原子。
8、根据权项7的方法,其中L代表羧基或烷基酯或其碱金属衍生物。
9、制备权项1-4中任何一个所定义的通式Ⅰ的二苯醚衍生物的方法,式中R4代表一个氢原子,包括具有CH2-CH2-OH取代基的前身化合物进行脱水。
11、根据权项5-10中任何一个的方法,实质上特别是前面例1和例2所述的方法。
12、根据权项5-11任何一个中的方法制备二苯醚衍生物。
13、除草剂组合物含有权项1-4和12任何一个中所要求的二苯醚衍生物以及一种载体。
14、根据权项13中的组合物,其中含有至少两种载体,两种中至少有一种是表面活性剂。
15、在一定地区防除杂草生长的方法,其中包括用权项1-4和12任何一个中所要求的二苯醚衍生物或权项13或14中所要求的组合物来处理杂草生长的地区。
16、使用权项1-4和12任何一个中所述的二苯醚衍生物作为除草剂。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8526612A GB2182328B (en) | 1985-10-29 | 1985-10-29 | Diphenyl ether derivatives |
CA000533923A CA1327811C (en) | 1985-10-29 | 1987-04-06 | Diphenyl ether derivatives |
EP87200698A EP0286735B1 (en) | 1985-10-29 | 1987-04-14 | Diphenyl ether derivatives |
BR8702010A BR8702010A (pt) | 1985-10-29 | 1987-04-27 | Derivados de eter difenilico,processo para a preparacao de derivado de eter difenilico,para composicao herbicida e processo combater o crescimento indesejado de plantas |
Publications (2)
Publication Number | Publication Date |
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CN87103167A true CN87103167A (zh) | 1988-11-16 |
CN1020728C CN1020728C (zh) | 1993-05-19 |
Family
ID=27425196
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Application Number | Title | Priority Date | Filing Date |
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CN87103167.1A Expired - Fee Related CN1020728C (zh) | 1985-10-29 | 1987-04-29 | 含二苯醚衍生物的除草组合物 |
Country Status (7)
Country | Link |
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EP (1) | EP0286735B1 (zh) |
CN (1) | CN1020728C (zh) |
AT (1) | ATE63910T1 (zh) |
CA (1) | CA1327811C (zh) |
DE (1) | DE3770458D1 (zh) |
ES (1) | ES2035849T3 (zh) |
GB (1) | GB2182328B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107188875A (zh) * | 2016-03-15 | 2017-09-22 | 联化科技股份有限公司 | 一种取代苯酞类化合物的制备方法及其中间体 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4911754A (en) * | 1987-07-16 | 1990-03-27 | American Cyanamid Company | Herbicidally active aryloxy saturated 5-membered benzo fused hetero-cyclic compounds |
GB8720509D0 (en) * | 1987-09-01 | 1987-10-07 | Shell Int Research | Diphenyl ether herbicides |
GB8720511D0 (en) * | 1987-09-01 | 1987-10-07 | Shell Int Research | Preparing diphenyl ethers |
US4960905A (en) * | 1987-09-21 | 1990-10-02 | Occidental Chemical Corporation | Phenoxy phthalic anhydrides |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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GB8522528D0 (en) * | 1985-09-11 | 1985-10-16 | Shell Int Research | Diphenyl ether herbicides |
-
1985
- 1985-10-29 GB GB8526612A patent/GB2182328B/en not_active Expired
-
1987
- 1987-04-06 CA CA000533923A patent/CA1327811C/en not_active Expired - Fee Related
- 1987-04-14 DE DE8787200698T patent/DE3770458D1/de not_active Expired - Fee Related
- 1987-04-14 ES ES198787200698T patent/ES2035849T3/es not_active Expired - Lifetime
- 1987-04-14 EP EP87200698A patent/EP0286735B1/en not_active Expired
- 1987-04-14 AT AT87200698T patent/ATE63910T1/de not_active IP Right Cessation
- 1987-04-29 CN CN87103167.1A patent/CN1020728C/zh not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107188875A (zh) * | 2016-03-15 | 2017-09-22 | 联化科技股份有限公司 | 一种取代苯酞类化合物的制备方法及其中间体 |
Also Published As
Publication number | Publication date |
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GB8526612D0 (en) | 1985-12-04 |
EP0286735A1 (en) | 1988-10-19 |
CN1020728C (zh) | 1993-05-19 |
DE3770458D1 (de) | 1991-07-04 |
EP0286735B1 (en) | 1991-05-29 |
GB2182328B (en) | 1989-09-20 |
CA1327811C (en) | 1994-03-15 |
ATE63910T1 (de) | 1991-06-15 |
ES2035849T3 (es) | 1993-05-01 |
GB2182328A (en) | 1987-05-13 |
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