CN1259321C - 取代苯基稠杂环类除草剂 - Google Patents
取代苯基稠杂环类除草剂 Download PDFInfo
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- CN1259321C CN1259321C CN 200310104881 CN200310104881A CN1259321C CN 1259321 C CN1259321 C CN 1259321C CN 200310104881 CN200310104881 CN 200310104881 CN 200310104881 A CN200310104881 A CN 200310104881A CN 1259321 C CN1259321 C CN 1259321C
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- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 12
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title abstract description 9
- 239000004009 herbicide Substances 0.000 title abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title abstract 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- -1 substituted-phenyl Chemical group 0.000 claims description 11
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 2
- 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 18
- 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
- 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
- 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 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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 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
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000005336 allyloxy group Chemical group 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
- 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
- FIWILGQIZHDAQG-UHFFFAOYSA-N NC1=C(C(=O)NCC2=CC=C(C=C2)OCC(F)(F)F)C=C(C(=N1)N)N1N=C(N=C1)C1(CC1)C(F)(F)F Chemical compound NC1=C(C(=O)NCC2=CC=C(C=C2)OCC(F)(F)F)C=C(C(=N1)N)N1N=C(N=C1)C1(CC1)C(F)(F)F FIWILGQIZHDAQG-UHFFFAOYSA-N 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
- 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
- 229910052801 chlorine Inorganic materials 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
- 229910052731 fluorine Inorganic materials 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
- 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
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- 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
本发明合成了取代苯基稠杂环类十二个超高效新结构除草剂，与以往国内外专利不同之处，在保留部分分子结构中取代苯基2-位氟、4-位氯原子和1-位的稠杂环具有的生物活性外，改变了5-位取代基团及杂环上的碳氧双键，使本发明得到的化合物具有超高效、低毒、高选择性等特点。
Description
[技术领域]
本发明属于精细化工农药除草剂。
[技术背景]
1987年，新化合物KIH-9201被发现，其结构式为：
该化合物适用的作物为玉米和大豆。
近年来，日本科研制药公司、组合化学公司、德国科尔公司、巴斯夫公司以及美国杜邦等公司，相继发明高效除草剂，如：ET-751、KIH-9210、KPP-300、KPP-314等。此类除草剂的分子结构中在苯环上的第1、2、4、5位上均有取代基，2、4位为卤素，1位与杂环相连。
由于人类对环境的重视，对农药毒性及对环境的影响，提出了更高的要求，因此化学农药进入“超高效、低毒、无污染”的新时期。
[发明内容]
本发明的目的就是开发研制无污染的超高效除草剂。
本发明为取代苯基稠杂环类除草剂，苯环的1位与杂环相连，其结构的最大特点在于：
1、苯环上5位分别由甲代烯丙氧基、N，N——二乙基磺酰基、N，N——二甲基磺酰基、甲氧羰基氯代乙烯基、烯丙氧基、甲氧羰基甲硫基等基团取代，也可与6位形成苯并呋喃。
2、苯环上4位由氯原子取代。
3、苯环上2位由氟原子、乙氧基取代。
以下合成了十二个新结构的高效除草剂，它们的结构为：
上述十二个新化合物属原卟啉原氧化酶抑制剂类除草剂，它们具有以下特点：
1、出色的除草作用。
2、抑制叶绿素生化合成。
3、抑制原卟啉原氧化酶及引起原卟啉IX的积累。
4、破坏类囊体膜的光氧化作用。
本发明化合物的合成方法如下：
1、苯并呋喃的合成
由2-氟-4-氯-5-甲代烯丙氧基苯胺经转位闭环制得相应的苯并呋喃化合物，即：
该反应分两步进行：
(a)甲代烯丙基转移到羟基的邻位，生成中间产品(B)；
(b)羟基加成到碳-碳双键上，生成产品(C)，反应在N，N-二乙基苯胺存在下经回流反应进行。闭环时用三氟甲基磺酸做催化剂。
2、化合物I杂环部分合成
整个反应以二氯甲烷做溶剂，分别用三乙胺、吡啶做催化剂，反应后催化剂用水洗去。
3、化合物XI杂环部分合成
4、化合物XII杂环部分合成
5、六氢哒嗪的合成
反应以乙醇做溶剂
由于四取代苯基杂环化合物以植物细胞的叶绿素为作用点，因此，确保了这类化合物在动、植物间的选择性，使其具有超高效、低毒的特点，与国外已发表的相关专利品种相比，具有相同或更高的除草效果，盆栽药效实验结果如下：
试验植物：
稗草(Echinochloa crusgalli)
苘麻(Abutilon thephrasti)
马唐(Digitaria sanguinalis)
苋菜(Acalypha austrlis)
狗尾草(Setaria viridis)
百日草(Zinnia elegans)
初筛数据表：
不同药剂不同用量对杂草鲜重抑制率(药后15天)
| 指标 | 稗草 | 马唐 | 狗尾 | 苋菜 | 苘麻 | |
| 化合物I | 1g(ai)/亩抑制率(％)10g(ai)/亩抑制率(％)100g(ai)/亩抑制率(％) | 42.7277.3687.68 | 81.2982.0396.87 | 62.9267.6193.38 | 100100100 | |
| 化合物II | 1g(ai)/亩抑制率(％)10g(ai)/亩抑制率(％)100g(ai)/亩抑制率(％) | 29.0753.7695.35 | 73.6178.5892.52 | 33.4825.9066.95 | 93.8695.1593.00 | |
| 化合物III | 1g(ai)/亩抑制率(％)10g(ai)/亩抑制率(％)100g(ai)/亩抑制率(％) | 58.9867.7270.45 | 24.0055.5675.00 | 0.6518.5054.11 | 75.2277.87100 | 100100100 |
| 化合物IV | 1g(ai)/亩抑制率(％)10g(ai)/亩抑制率(％)100g(ai)/亩抑制率(％) | 49.1665.6574.20 | 35.1150.8872.00 | 4.704.426.14 | 100100100 | 100100100 |
| 化合物V | 1g(ai)/亩抑制率(％)10g(ai)/亩抑制率(％)100g(ai)/亩抑制率(％) | 40.4043.4544.80 | 7.7012.0020.13 | 3.045.257.47 | 100100100 | 100100100 |
| 化合物VI | 1g(ai)/亩抑制率(％)10g(ai)/亩抑制率(％)100g(ai)/亩抑制率(％) | 58.8560.1390.02 | 67.1471.5399.01 | 5.6072.3096.80 | 100100100 | 100100100 |
| 化 | 1g(ai)/亩抑制率(％) | 54.57 | 73.19 | 64.64 | 100 | 100 |
| 合物VII | 10g(ai)/亩抑制率(％)100g(ai)/亩抑制率(％) | 52.9354.24 | 74.7275.08 | 88.3440.42 | 100100 | 100100 |
| 化合物VIII | 1g(ai)/亩抑制率(％)10g(ai)/亩抑制率(％)100g(ai)/亩抑制率(％) | 48.1084.3182.31 | 63.7174.5096.68 | 40.4264.1397.11 | 100100100 | 100100100 |
| 化合物IX | 1g(ai)/亩抑制率(％)10g(ai)/亩抑制率(％)100g(ai)/亩抑制率(％) | 50.2365.4180.88 | 61.3279.3892.99 | 32.4968.5591.32 | 100100100 | 100100100 |
| 化合物XII | 1g(ai)/亩抑制率(％)10g(ai)/亩抑制率(％)100g(ai)/亩抑制率(％) | 45.8360.4985.78 | 50.9271.0089.34 | 46.1373.2088.56 | 100100100 | 100100100 |
初筛实验数据表明，本专利发明的十二个化合物均具有较高的除草活性，对阔叶草的防效优于禾本科杂草，在低浓度1gai/亩时差别比较明显，证明其具有较高的选择性，在此实验基础上，选择阔叶草进行复筛。
复筛数据表：
不同药剂不同用量对杂草鲜重抑制率(药后15天)
| 指标 | 百日草(％) | 苘麻(％) | 苋草(％) | |
| KIH9201 | 0.25g(ai)/亩0.5g(ai)/亩1g(ai)/亩2g(ai)/亩4g(ai)/亩 | 96.1795.7295.3395.7496.56 | 72.5078.1483.2873.6978.54 | 59.9486.1789.1176.5295.27 |
| 化合物I | 0.25g(ai)/亩0.5g(ai)/亩1g(ai)/亩2g(ai)/亩4g(ai)/亩 | 52.3290.3695.9584.0096.30 | 70.1373.5973.6979.1375.77 | 17.3332.8620.0866.3893.66 |
| 化合物II | 0.25g(ai)/亩0.5g(ai)/亩1g(ai)/亩2g(ai)/亩4g(ai)/亩 | 59.2785.2558.1474.3787.23 | 79.5376.8664.1969.6373.79 | 44.8918.6634.0030..222.16 |
| 化合物III | 0.25g(ai)/亩0.5g(ai)/亩1g(ai)/亩2g(ai)/亩4g(ai)/亩 | 48.1335.7672.5987.2195.53 | 58.9546.9868.3567.4672.40 | -2.08-3.415.689.9463.07 |
| 化合物IV | 0.25g(ai)/亩0.5g(ai)/亩1g(ai)/亩2g(ai)/亩4g(ai)/亩 | 34.8677.3177.0993.8095.36 | 62.1172.7076.5672.9071.71 | 38.3512.6964.3972.0674.05 |
| 化合物V | 0.25g(ai)/亩0.5g(ai)/亩1g(ai)/亩2g(ai)/亩4g(ai)/亩 | 75.5097.4495.5597.3196.71 | 64.1975.1770.5277.3579.03 | 73.8661.6587.5992.1494.22 |
| 化合物VI | 0.25g(ai)/亩0.5g(ai)/亩1g(ai)/亩2g(ai)/亩4g(ai)/亩 | 84.4688.2997.1593.7797.84 | 75.0774.6876.1673.5977.15 | 24.4360.5125.7649.9188.73 |
| 化合物VII | 0.25g(ai)/亩0.5g(ai)/亩1g(ai)/亩2g(ai)/亩4g(ai)/亩 | 87.5897.0996.4894.5896.31 | 72.4078.2480.3280.2273.79 | 33.5227.0861.6571.4088.45 |
| 化合物VIII | 0.25g(ai)/亩0.5g(ai)/亩1g(ai)/亩2g(ai)/亩4g(ai)/亩 | 69.3490.2395.4496.7996.23 | 64.4973.9878.4576.3779.72 | 36.7965.3785.3488.2993.35 |
| 化合物IX | 0.25g(ai)/亩0.5g(ai)/亩1g(ai)/亩2g(ai)/亩4g(ai)/亩 | 60.7389.2591.3993.7799.20 | 70.3975.6179.8380.2584.96 | 56.3145.2965.9873.6688.37 |
| 化合物X | 0.25g(ai)/亩0.5g(ai)/亩1g(ai)/亩2g(ai)/亩4g(ai)/亩 | 80.2595.3694.4997.3598.20 | 73.3876.4275.9379.4078.95 | 37.7665.1970.3881.2690.67 |
| 化合物XI | 0.25g(ai)/亩0.5g(ai)/亩1g(ai)/亩2g(ai)/亩4g(ai)/亩 | 75.3990.2295.7495.3897.25 | 78.3482.9893.2096.7894.77 | 66.3280.4686.7787.9896.00 |
由复筛数据可见：
化合物V、VI、VII、VIII、IX、X、XI在1gai/亩的剂量下仍可有效抑制百日草、苘麻、苋菜的生长，是超高效的除草剂。
[具体实施方式]
以下给出五个实施例，来进一步说明本发明。
实施例一
化合物I的合成
在1000ml四口瓶中投入4-氯-2-氟-5(2-甲基-2-丙烯基)氧基苯基氨基甲酸乙酯81g(99.3％0.28ml)，40％氢氧化钠溶液60克(0.6ml)、乙醇300ml搅拌加热至回流3小时，冷却用稀盐酸中和至PH＝5-6，蒸馏脱乙醇。釜残用200ml；二氯甲烷萃取，分出水层，得到4-氯-2-氟-5-(2-甲基-2-丙烯基)苯胺的二氯甲烷溶液。在此溶液中投入硫光气37.3克(95％，0.31ml)，三乙胺62.6克(0.62ml)，低温反应30分钟，反应完毕后用150ml水洗三遍，有机相加入六氢哒嗪27克(0.31ml)补加二氯甲烷100ml，室温反应30分钟，然后向此溶液中加入吡啶45.3克(0.62ml)，和固体光气30.7克(0.31ml)，低温反应30分钟，反应完毕后用150ml水洗三次，有机相脱溶，冷却后得到产品化合物I，烘干恒重64克，浅黄色粉末，纯度97.4％，收率61.9％，熔点98--99℃，结构经H-NMR确认正确。
实施例二
化合物II的合成
在250ml四口瓶中加入100ml乙醇，2-氯-4-氟-5-乙酰替氨基苯基-N，N-二乙基磺酰胺7.0克(90.5％，0.02ml)，氢氧化钠8.4克(40％水溶液，0.084ml)加热回流三小时，反应完全用稀盐酸中和，常压脱乙醇，釜残用60ml二氯甲烷萃取，得到5-氨基-2-氯-4-2氧基苯基-N，N-二乙醛磺酰胺的二氯甲烷溶液.向此溶液加入硫光气2.4克(95％，0.02ml)、三乙胺4.0克(0.04ml)反应30分钟，用水洗三遍，有机相加入六氢哒嗪4.1克，室温反应30分钟，然后加入吡啶，固体光气，低温反应30分钟，用100ml水洗三遍，有机相脱溶，得到化合物II，经柱层析(乙酸乙酯∶正己烷＝1∶1)提纯，得到2.5克浅黄色晶体纯度99.7％，收率28.7％，熔点109--111℃，结构经H-NMR确认正确。
实施例三
化合物III的合成
在250ml四口瓶中投入二氯甲烷100ml，4-氨基-7-氯-5-氟-2.2-二甲基苯并呋喃24克(85％，0.1ml)、硫光气13.8克(0.12ml)、三乙胺24.4克(0.24ml)，低温反应30分钟，用100ml水洗三次，有机相中加入六氢哒嗪20.6克(50％，0.12ml)，室温反应30分钟，然后加入29.2克吡啶(0.4ml)，固体光气29.7克(0.3ml)，低温反应30分钟，用100ml水洗三遍，有机相脱溶，得到化合物III，在100ml乙醇中重结晶，得到20克土黄色粉末状固体，含量99.9％，收率55.9％，熔点152--156℃，结构经H-NMR确认正确。
实施例四
化合物IX的合成
在250ml四口瓶中投入4-氯-2-氟-5-(2-丙烯基氧基)苯胺5克，二氯甲烷40克，硫光气4克，三乙胺4.8克，低温反应30分钟，然后用100ml水洗三次，有机相中加入六氢哒嗪4.5克，室温反应30分钟，向此溶液中加入吡啶6.1克，硫光气4.6克，低温反应30分钟，用100ml水洗三遍，有机相脱溶，得釜残11克，经柱层析(乙酸乙酯∶正己烷＝1∶1)提纯，得到产品化合物IX，熔点141℃，结构H-NMR确认正确。
实施例五
化合物XII的合成
在250ml四口瓶中投入5-氨基-2-氯-4-氟苯基硫代乙酸甲酯5.9克，二氯甲烷40克，硫光气4克，三乙胺4.8克，低温反应30分钟，然后用100ml水洗三次，有机相中加入六氢哒嗪3.5克，室温反应30分钟，然后加入吡啶6.1克，氯乙酰氯5克，低温反应30分钟，用100ml水洗三遍，有机相脱溶，得釜残8克，经柱层析(乙酸乙酯∶甲苯∶正己烷＝1∶4∶1)提纯，得到产品化合物XII，熔点128--129℃，结构H-NMR确认正确。
Claims (1)
1、一种取代苯基稠杂环类除草剂，其特征是：它选自以下12个化合物：
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| CN 200310104881 CN1259321C (zh) | 2003-10-21 | 2003-10-21 | 取代苯基稠杂环类除草剂 |
| PCT/CN2004/001176 WO2005037844A1 (fr) | 2003-10-21 | 2004-10-18 | Heterocycles condenses a substitution phenyle comme herbicides tres efficaces |
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| CN102286005A (zh) * | 2011-07-01 | 2011-12-21 | 南京工业大学 | 一种合成氟噻乙草酯的方法 |
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| DE3675931D1 (de) * | 1986-03-25 | 1991-01-10 | Kumiai Chemical Industry Co | Thiadiazabicyclononanderivate, verfahren zu ihrer herstellung und herbizide zusammensetzungen. |
| KR100225838B1 (ko) * | 1992-07-10 | 1999-10-15 | 모치츠키 노부히코 | 제초제 조성물 |
| JPH0859642A (ja) * | 1994-08-22 | 1996-03-05 | Mitsubishi Chem Corp | ３，４−アルキレン−１，３，４−チアジアゾリジン−２−オン類の製造方法 |
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| CN102286005A (zh) * | 2011-07-01 | 2011-12-21 | 南京工业大学 | 一种合成氟噻乙草酯的方法 |
| CN102286005B (zh) * | 2011-07-01 | 2013-12-25 | 南京工业大学 | 一种合成氟噻乙草酯的方法 |
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