CN1609110A - High efficiency substituted benzene fused heterocycle herbicides - Google Patents
High efficiency substituted benzene fused heterocycle herbicides Download PDFInfo
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- CN1609110A CN1609110A CN 200310104881 CN200310104881A CN1609110A CN 1609110 A CN1609110 A CN 1609110A CN 200310104881 CN200310104881 CN 200310104881 CN 200310104881 A CN200310104881 A CN 200310104881A CN 1609110 A CN1609110 A CN 1609110A
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- high efficiency
- inhibiting rate
- fused heterocycle
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- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 13
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 10
- 239000004009 herbicide Substances 0.000 title claims abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title abstract 4
- 231100000053 low toxicity Toxicity 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 3
- -1 substituted-phenyl Chemical group 0.000 claims description 13
- 125000005336 allyloxy group Chemical group 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 19
- 230000002401 inhibitory effect Effects 0.000 description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- HTFFABIIOAKIBH-UHFFFAOYSA-N diazinane Chemical compound C1CCNNC1 HTFFABIIOAKIBH-UHFFFAOYSA-N 0.000 description 6
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 5
- 230000002363 herbicidal effect Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 240000006995 Abutilon theophrasti Species 0.000 description 4
- 240000001592 Amaranthus caudatus Species 0.000 description 4
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 4
- 240000003307 Zinnia violacea Species 0.000 description 4
- 235000012735 amaranth Nutrition 0.000 description 4
- 239000004178 amaranth Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 244000025254 Cannabis sativa Species 0.000 description 3
- 244000058871 Echinochloa crus-galli Species 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229930002875 chlorophyll Natural products 0.000 description 2
- 235000019804 chlorophyll Nutrition 0.000 description 2
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003389 potentiating effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FMCAFXHLMUOIGG-IWFBPKFRSA-N (2s)-2-[[(2s)-2-[[(2s)-2-[[(2r)-2-formamido-3-sulfanylpropanoyl]amino]-3-methylbutanoyl]amino]-3-(4-hydroxy-2,5-dimethylphenyl)propanoyl]amino]-4-methylsulfanylbutanoic acid Chemical compound O=CN[C@@H](CS)C(=O)N[C@@H](C(C)C)C(=O)N[C@H](C(=O)N[C@@H](CCSC)C(O)=O)CC1=CC(C)=C(O)C=C1C FMCAFXHLMUOIGG-IWFBPKFRSA-N 0.000 description 1
- FWNGNMWNTIIKRE-UHFFFAOYSA-N 2-amino-n,n-diethylbenzenesulfonamide Chemical compound CCN(CC)S(=O)(=O)C1=CC=CC=C1N FWNGNMWNTIIKRE-UHFFFAOYSA-N 0.000 description 1
- ASKPAMCKVMWJCA-UHFFFAOYSA-N 4-chloro-2-fluoro-5-(2-methylprop-2-enyl)aniline Chemical compound ClC1=CC(=C(N)C=C1CC(=C)C)F ASKPAMCKVMWJCA-UHFFFAOYSA-N 0.000 description 1
- GKULOLQQCOAMEL-UHFFFAOYSA-N 7-chloro-5-fluoro-2,2-dimethyl-3H-1-benzofuran-4-amine Chemical compound ClC1=CC(F)=C(N)C2=C1OC(C)(C)C2 GKULOLQQCOAMEL-UHFFFAOYSA-N 0.000 description 1
- 241000219144 Abutilon Species 0.000 description 1
- 241001060350 Acalypha Species 0.000 description 1
- IKDIJXDZEYHZSD-UHFFFAOYSA-N Ameisensaeure-phenaethylester Natural products O=COCCC1=CC=CC=C1 IKDIJXDZEYHZSD-UHFFFAOYSA-N 0.000 description 1
- 241000981770 Buddleja asiatica Species 0.000 description 1
- KSFOVUSSGSKXFI-GAQDCDSVSA-N CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O Chemical compound CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O KSFOVUSSGSKXFI-GAQDCDSVSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 244000152970 Digitaria sanguinalis Species 0.000 description 1
- 235000010823 Digitaria sanguinalis Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229940087098 Oxidase inhibitor Drugs 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 235000011999 Panicum crusgalli Nutrition 0.000 description 1
- 240000003461 Setaria viridis Species 0.000 description 1
- 235000002248 Setaria viridis Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 150000001907 coumarones Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- ZCNQYNHDVRPZIH-UHFFFAOYSA-N fluthiacet-methyl Chemical compound C1=C(Cl)C(SCC(=O)OC)=CC(N=C2N3CCCCN3C(=O)S2)=C1F ZCNQYNHDVRPZIH-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 229950003776 protoporphyrin Drugs 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 210000002377 thylakoid Anatomy 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Classifications
-
- 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention is 12 kinds of high efficiency substituted benzene fused heterocycle herbicides. The present invention features that the substituted group in 5-place and C-O double bond in heterocycle are altered while preserving the bioactivity of phenyl-substituting fluorine atom in 2-place, chlorine atom in 4-place and fused heterocycle in 1-place, so that the compounds of the present invention has high efficiency, low toxicity, high selectivity and other features.
Description
[technical field]
The invention belongs to the fine chemistry industry pesticide herbicide.
[technical background]
1987, new compound KIH-9201 was found, and its structural formula is:
The crop that this compound is suitable for is corn and soybean.
In recent years, company such as Japanese scientific research drugmaker, combinatorial chemistry company, German Ker Co.,Ltd, BASF AG and Dupont, invention highy potent herbicide in succession, as: ET-751, KIH-9210, KPP-300, KPP-314 etc.On the 1st, 2,4,5 on the phenyl ring substituting group is arranged all in the molecular structure of this type of weedicide, 2,4 is halogen, and 1 links to each other with heterocycle.
Because human attention,, have higher requirement, so chemical pesticide enters the new period of " ultra-high efficiency, low toxicity, pollution-free " to toxicity of pesticide and to the influence of environment to environment.
[summary of the invention]
Purpose of the present invention is developed free of contamination ultra-high efficiency weedicide exactly.
The present invention is a substituted-phenyl fused heterocycle type weedicide, and 1 of phenyl ring links to each other with heterocycle, and the maximum characteristics of its structure are:
1, on the phenyl ring 5 respectively by first for allyloxy, N, N-diethyl alkylsulfonyl, N, groups such as N-dimethyl methyl acyl group, methoxycarbonyl chloro vinyl, allyloxy, methoxycarbonyl methylthio group replace, also can with 6 form cumarones.
2, on the phenyl ring 4 replace by the chlorine atom.
3, on the phenyl ring 2 replace by fluorine atom, oxyethyl group.
Below synthesized the highy potent herbicide of 12 new textures, their structure is:
Above-mentioned 12 new compounds belong to proporphyrinogen oxidase inhibitor class weedicide, and they have following characteristics:
1, outstanding herbicide effect.
2, suppressing chlorophyll biochemistry synthesizes.
3, suppress proporphyrinogen oxidase and cause the accumulation of protoporphyrin IX.
4, destroy the photooxidation of thylakoid membrane.
The synthetic method of The compounds of this invention is as follows:
1, cumarone is synthetic
Make corresponding benzofuran compound for allyloxy aniline through the transposition closed loop by 2-fluoro-4-chloro-5-first, that is:
This reaction is carried out in two steps:
(a) methylallyl is transferred to the ortho position of hydroxyl, generates intermediates (B);
(b) hydroxyl adds on the carbon-to-carbon double bond, generates product (C), is reflected at N, the N-diethyl
Aniline carries out through back flow reaction under existing.Make catalyzer with trifluoromethane sulfonic acid during closed loop.
2, compound I heterocyclic moiety is synthetic
Entire reaction is made solvent with methylene dichloride, makees catalyzer with 32 amine, pyridine respectively, post catalyst reaction water flush away.
3, compounds X I heterocyclic moiety is synthetic
4, compounds X II heterocyclic moiety is synthetic
5, hexahydro-pyridazine is synthetic
Reaction is made solvent with ethanol
Because the tetra-substituted phenyl heterogeneous ring compound is a point of application with the chlorophyll of vegetable cell, therefore, guaranteed the selectivity of this compounds between animal and plant, make it have the characteristics of ultra-high efficiency, low toxicity, compare with the relevant patent kind of abroad having delivered, have identical or higher herbicidal effect, potted plant effect experiment result is as follows:
Test plant:
Barnyard grass grass (Echinochloa crusgalli)
Piemarker (Abutilon thephrasti)
Lady's-grass (Digitaria sanguinalis)
Three-coloured amaranth (Acalypha austrlis)
Herba Setariae Viridis (Setaria viridis)
Youth-and-old-age (Zinnia elegans)
The primary dcreening operation data sheet:
Different medicament different amounts are to weeds fresh weight inhibiting rate (behind the medicine 15 days)
| Index | The barnyard grass grass | Lady's-grass | The dog tail | Three-coloured amaranth | Piemarker |
| Change 1g (ai)/mu inhibiting rate (%) and close 10g (ai)/mu inhibiting rate (%) thing 100g (ai)/mu inhibiting rate (%) I | ??42.72 ??77.36 ??87.68 | ??81.29 ??82.03 ??96.87 | ??62.92 ??67.61 ??93.38 | ??100 ??100 ??100 | |
| Change 1g (ai)/mu inhibiting rate (%) and close 10g (ai)/mu inhibiting rate (%) thing 100g (ai)/mu inhibiting rate (%) II | ??29.07 ??53.76 ??95.35 | ??73.61 ??78.58 ??92.52 | ??33.48 ??25.90 ??66.95 | ??93.86 ??95.15 ??93.00 | |
| Change 1g (ai)/mu inhibiting rate (%) and close 10g (ai)/mu inhibiting rate (%) thing 100g (ai)/mu inhibiting rate (%) III | ??58.98 ??67.72 ??70.45 | ??24.00 ??55.56 ??75.00 | ??0.65 ??18.50 ??54.11 | ??75.22 ??77.87 ??100 | ??100 ??100 ??100 |
| Change 1g (ai)/mu inhibiting rate (%) and close 10g (ai)/mu inhibiting rate (%) thing 100g (ai)/mu inhibiting rate (%) IV | ??49.16 ??65.65 ??74.20 | ??35.11 ??50.88 ??72.00 | ??4.70 ??4.42 ??6.14 | ??100 ??100 ??100 | ??100 ??100 ??100 |
| Change 1g (ai)/mu inhibiting rate (%) and close 10g (ai)/mu inhibiting rate (%) thing 100g (ai)/mu inhibiting rate (%) V | ??40.40 ??43.45 ??44.80 | ??7.70 ??12.00 ??20.13 | ??3.04 ??5.25 ??7.47 | ??100 ??100 ??100 | ??100 ??100 ??100 |
| Change 1g (ai)/mu inhibiting rate (%) and close 10g (ai)/mu inhibiting rate (%) thing 100g (ai)/mu inhibiting rate (%) VI | ??58.85 ??60.13 ??90.02 | ??67.14 ??71.53 ??99.01 | ??5.60 ??72.30 ??96.80 | ??100 ??100 ??100 | ??100 ??100 ??100 |
| Change 1g (ai)/mu inhibiting rate (%) | ??54.57 | ??73.19 | ??64.64 | ??100 | ??100 |
| Close 10g (ai)/mu inhibiting rate (%) thing 100g (ai)/mu inhibiting rate (%) VII | ??52.93 ??54.24 | ??74.72 ??75.08 | ??88.34 ??40.42 | ??100 ??100 | ??100 ??100 |
| Change 1g (ai)/mu inhibiting rate (%) and close 10g (ai)/mu inhibiting rate (%) thing 100g (ai)/mu inhibiting rate (%) VIII | ??48.10 ??84.31 ??82.31 | ??63.71 ??74.50 ??96.68 | ??40.42 ??64.13 ??97.11 | ??100 ??100 ??100 | ??100 ??100 ??100 |
| Change 1g (ai)/mu inhibiting rate (%) and close 10g (ai)/mu inhibiting rate (%) thing 100g (ai)/mu inhibiting rate (%) IX | ??50.23 ??65.41 ??80.88 | ??61.32 ??79.38 ??92.99 | ??32.49 ??68.55 ??91.32 | ??100 ??100 ??100 | ??100 ??100 ??100 |
| Change 1g (ai)/mu inhibiting rate (%) and close 10g (ai)/mu inhibiting rate (%) thing 100g (ai)/mu inhibiting rate (%) XII | ??45.83 ??60.49 ??85.78 | ??50.92 ??71.00 ??89.34 | ??46.13 ??73.20 ??88.56 | ??100 ??100 ??100 | ??100 ??100 ??100 |
The primary dcreening operation experimental data shows, 12 compounds of this patent invention all have higher weeding activity, and the preventive effect of broadleaved herb is better than gramineous weeds, difference is apparent in view when lower concentration 1gai/ mu, prove that it has higher selectivity, on this experiment basis, select broadleaved herb to carry out multiple sieve.
Sieve data sheet again:
Different medicament different amounts are to weeds fresh weight inhibiting rate (behind the medicine 15 days)
| Index | Youth-and-old-age (%) | Piemarker (%) | Amaranth grass (%) |
| 0.25g (ai)/mu KIH9201 0.5g (ai)/mu 1g (ai)/mu 2g (ai)/mu 4g (ai)/mu | ????96.17 ????95.72 ????95.33 ????95.74 ????96.56 | ????72.50 ????78.14 ????83.28 ????73.69 ????78.54 | ????59.94 ????86.17 ????89.11 ????76.52 ????95.27 |
| 0.25g (ai)/muization 0.5g (ai)/mu closes 1g (ai)/mu thing 2g (ai)/mu I 4g (ai)/mu | ????52.32 ????90.36 ????95.95 ????84.00 ????96.30 | ????70.13 ????73.59 ????73.69 ????79.13 ????75.77 | ????17.33 ????32.86 ????20.08 ????66.38 ????93.66 |
| 0.25g (ai)/muization 0.5g (ai)/mu closes 1g (ai)/mu thing 2g (ai)/mu II 4g (ai)/mu | ????59.27 ????85.25 ????58.14 ????74.37 ????87.23 | ????79.53 ????76.86 ????64.19 ????69.63 ????73.79 | ????44.89 ????18.66 ????34.00 ????30..2 ????22.16 |
| 0.25g (ai)/muization 0.5g (ai)/mu closes 1g (ai)/mu thing 2g (ai)/mu III 4g (ai)/mu | ????48.13 ????35.76 ????72.59 ????87.21 ????95.53 | ????58.95 ????46.98 ????68.35 ????67.46 ????72.40 | ???-2.08 ???-3.41 ????5.68 ????9.94 ????63.07 |
| 0.25g (ai)/muization 0.5g (ai)/mu closes 1g (ai)/mu thing 2g (ai)/mu IV 4g (ai)/mu | ????34.86 ????77.31 ????77.09 ????93.80 ????95.36 | ????62.11 ????72.70 ????76.56 ????72.90 ????71.71 | ????38.35 ????12.69 ????64.39 ????72.06 ????74.05 |
| 0.25g (ai)/muization 0.5g (ai)/mu closes 1g (ai)/mu thing 2g (ai)/mu V 4g (ai)/mu | ????75.50 ????97.44 ????95.55 ????97.31 ????96.71 | ????64.19 ????75.17 ????70.52 ????77.35 ????79.03 | ????73.86 ????61.65 ????87.59 ????92.14 ????94.22 |
| 0.25g (ai)/muization 0.5g (ai)/mu closes 1g (ai)/mu thing 2g (ai)/mu VI 4g (ai)/mu | ????84.46 ????88.29 ????97.15 ????93.77 ????97.84 | ????75.07 ????74.68 ????76.16 ????73.59 ????77.15 | ????24.43 ????60.51 ????25.76 ????49.91 ????88.73 |
| 0.25g (ai)/muization 0.5g (ai)/mu closes 1g (ai)/mu thing 2g (ai)/mu VII 4g (ai)/mu | ????87.58 ????97.09 ????96.48 ????94.58 ????96.31 | ????72.40 ????78.24 ????80.32 ????80.22 ????73.79 | ????33.52 ????27.08 ????61.65 ????71.40 ????88.45 |
| 0.25g (ai)/muization 0.5g (ai)/mu closes 1g (ai)/mu thing 2g (ai)/mu VIII 4g (ai)/mu | ????69.34 ????90.23 ????95.44 ????96.79 ????96.23 | ????64.49 ????73.98 ????78.45 ????76.37 ????79.72 | ????36.79 ????65.37 ????85.34 ????88.29 ????93.35 |
| 0.25g (ai)/muization 0.5g (ai)/mu closes 1g (ai)/mu thing 2g (ai)/mu IX 4g (ai)/mu | ????60.73 ????89.25 ????91.39 ????93.77 ????99.20 | ????70.39 ????75.61 ????79.83 ????80.25 ????84.96 | ????56.31 ????45.29 ????65.98 ????73.66 ????88.37 |
| 0.25g (ai)/muization 0.5g (ai)/mu closes 1g (ai)/mu thing 2g (ai)/mu X 4g (ai)/mu | ????80.25 ????95.36 ????94.49 ????97.35 ????98.20 | ????73.38 ????76.42 ????75.93 ????79.40 ????78.95 | ????37.76 ????65.19 ????70.38 ????81.26 ????90.67 |
| 0.25g (ai)/muization 0.5g (ai)/mu closes 1g (ai)/mu thing 2g (ai)/mu XI 4g (ai)/mu | ????75.39 ????90.22 ????95.74 ????95.38 ????97.25 | ????78.34 ????82.98 ????93.20 ????96.78 ????94.77 | ????66.32 ????80.46 ????86.77 ????87.98 ????96.00 |
By sieving data again as seen:
Compound V, VI, VII, VIII, IX, X, XI still can effectively suppress the growth of youth-and-old-age, piemarker, three-coloured amaranth under the dosage of 1gai/ mu, be the weedicide of ultra-high efficiency.
[embodiment]
Below provide five embodiment, advance-go on foot explanation the present invention.
Embodiment one
Synthesizing of Compound I
In the 1000ml four-hole bottle, drop into 4-chloro-2-fluoro-5 (2-methyl-2-propenyl) methoxy phenyl ethyl formate 81g (99.3%0.28ml), 40% sodium hydroxide solution, 60 grams (0.6ml), ethanol 300ml are heated with stirring to and refluxed 3 hours, cooling is neutralized to PH=5-6 with dilute hydrochloric acid, and ethanol is taken off in distillation.The residual 200ml that uses of still; Dichloromethane extraction divides water-yielding stratum, obtains the dichloromethane solution of 4-chloro-2-fluoro-5-(2-methyl-2-propenyl) aniline.In this solution, drop into thiophosgene 37.3 grams (95%, 0.31ml), triethylamine 62.6 grams (0.62ml), low-temp reaction 30 minutes is washed three times with 150ml after reaction finishes, organic phase adds hexahydro-pyridazine 27 grams (0.31ml) and adds methylene dichloride 100ml, room temperature reaction 30 minutes adds pyridine 45.3 grams (0.62ml) and solid phosgene 30.7 grams (0.31ml) then in this solution, low-temp reaction 30 minutes, with 150ml washing three times, the organic phase precipitation obtained product compound I after the cooling after reaction finished, oven dry constant weight 64 grams, buff powder, purity 97.4%, yield 61.9%, fusing point 98--99 ℃, structure is confirmed correct through H-NMR.
Embodiment two
Compound I I's is synthetic
In the 250ml four-hole bottle, add 100ml ethanol, 2-chloro-4-fluoro-5-acetyl is for aminophenyl-N, N-diethyl sulphonamide 7.0 grams (90.5%, 0.02ml), sodium hydroxide 8.4 gram (40% aqueous solution, 0.084ml) reflux three hours, react completely with the dilute hydrochloric acid neutralization, normal pressure takes off ethanol, the residual 60ml dichloromethane extraction of using of still, obtain 5-amino-2-chloro-4-2 oxygen base phenyl-N, the dichloromethane solution of N-two acetaldehyde sulphonamide.Add thiophosgene 2.4 grams (95% to this solution, 0.02ml), triethylamine 4.0 gram (0.04ml) reaction 30 minutes, water is given a baby a bath on the third day after its birth time, organic phase adds hexahydro-pyridazine 4.1 grams, room temperature reaction 30 minutes, add pyridine then, solid phosgene, low-temp reaction 30 minutes, with 100ml washing three times, the organic phase precipitation obtains Compound I I, through column chromatography (ethyl acetate: normal hexane=1: 1) purify, obtain 2.5 gram pale yellow crystals purity 99.7%, yield 28.7%, fusing point 109--111 ℃, structure is confirmed correct through H-NMR.
Embodiment three
Synthesizing of compound III
In the 250ml four-hole bottle, drop into methylene dichloride 100ml, 4-amino-7-chloro-5-fluoro-2.2-dimethyl benzofuran 24 grams (85%, 0.1ml), thiophosgene 13.8 grams (0.12ml), triethylamine 24.4 grams (0.24ml), low-temp reaction 30 minutes, with 100ml washing three times, adding hexahydro-pyridazine 20.6 grams in the organic phase (50%, 0.12ml), room temperature reaction 30 minutes, add 29.2 gram pyridines (0.4ml) then, solid phosgene 29.7 grams (0.3ml), low-temp reaction 30 minutes is with 100ml washing three times, the organic phase precipitation, obtain compound III, recrystallization in 100ml ethanol obtains 20 gram khaki color pulverulent solids, content 99.9%, yield 55.9%, fusing point 152--156 ℃, structure is confirmed correct through H-NMR.
Embodiment four
Compound I X's is synthetic
In the 250ml four-hole bottle, drop into 4-chloro-2-fluoro-5-(2-propenyl oxygen base) aniline 5 grams, methylene dichloride 40 grams, thiophosgene 4 grams, triethylamine 4.8 grams, low-temp reaction 30 minutes is then with 100ml washing three times, add hexahydro-pyridazine 4.5 grams in the organic phase, room temperature reaction 30 minutes adds pyridine 6.1 grams in this solution, thiophosgene 4.6 grams, low-temp reaction 30 minutes, with 100ml washing three times, organic phase precipitation, get residual 11 grams of still, through column chromatography (ethyl acetate: normal hexane=1: 1) purify, obtain product compound IX, 141 ℃ of fusing points, structure H-NMR confirms correct.
Embodiment five
Compounds X II's is synthetic
In the 250ml four-hole bottle, drop into 5-amino-2-chloro-4-fluorophenyl thio acetate 5.9 grams, methylene dichloride 40 grams, thiophosgene 4 grams, triethylamine 4.8 grams, low-temp reaction 30 minutes is then with 100ml washing three times, add hexahydro-pyridazine 3.5 grams in the organic phase, room temperature reaction 30 minutes adds pyridine 6.1 grams then, chloroacetyl chloride 5 grams, low-temp reaction 30 minutes, with 100ml washing three times, organic phase precipitation, get residual 8 grams of still, through column chromatography (ethyl acetate: toluene: normal hexane=1: 4: 1) purify, obtain product compound XII, fusing point 128--129 ℃, structure H-NMR confirms correct.
Claims (1)
1, a kind of substituted-phenyl fused heterocycle type ultra-high efficiency weedicide; it is characterized in that: 1 is connected with fused heterocycle on the molecular structure phenyl ring of this weedicide; 2,4 are replaced by fluorine atom, chlorine atom, oxyethyl group respectively; on the phenyl ring 5 respectively by first for allyloxy, N; N---diethyl alkylsulfonyl, N; N---dimethyl methyl acyl group furyl, methoxycarbonyl, chloro vinyl, methoxycarbonyl methylthio group, allyl group replace, thereby obtain 12 ultra-high efficiency low toxicity herbicides.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310104881 CN1259321C (en) | 2003-10-21 | 2003-10-21 | High efficiency substituted benzene fused heterocycle herbicides |
| PCT/CN2004/001176 WO2005037844A1 (en) | 2003-10-21 | 2004-10-18 | Substituted phenyl fused heterocycles as high efficiency herbicides |
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| CN 200310104881 CN1259321C (en) | 2003-10-21 | 2003-10-21 | High efficiency substituted benzene fused heterocycle herbicides |
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| CN1259321C CN1259321C (en) | 2006-06-14 |
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| CN113698421A (en) * | 2020-05-20 | 2021-11-26 | 南开大学 | Thiadiazole isoxazoline compound, preparation method and application thereof, and herbicide |
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| CN102286005B (en) * | 2011-07-01 | 2013-12-25 | 南京工业大学 | Method for synthesizing fluthiacet-ethyl |
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| EP0238711B1 (en) * | 1986-03-25 | 1990-11-28 | Kumiai Chemical Industry Co., Ltd. | Thiadiazabicyclononane derivatives, processes for their production and herbizidal compositions |
| ES2105290T3 (en) * | 1992-07-10 | 1997-10-16 | Kumiai Chemical Industry Co | HERBICIDE COMPOSITION. |
| JPH0859642A (en) * | 1994-08-22 | 1996-03-05 | Mitsubishi Chem Corp | Production of 3,4-alkylene-1,3,4-thiadiazolidin-2-ones |
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| CN113698421A (en) * | 2020-05-20 | 2021-11-26 | 南开大学 | Thiadiazole isoxazoline compound, preparation method and application thereof, and herbicide |
| CN113698421B (en) * | 2020-05-20 | 2024-07-30 | 南开大学 | Thiadiazole isoxazoline compound, preparation method and application thereof, and herbicide |
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| WO2005037844A1 (en) | 2005-04-28 |
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