CN86104887A - (r)-2-[4-(5-氯-3-氟吡啶-2-基氧)苯氧基]丙酸炔丙基酯的制备方法及其作为除草剂的应用 - Google Patents
(r)-2-[4-(5-氯-3-氟吡啶-2-基氧)苯氧基]丙酸炔丙基酯的制备方法及其作为除草剂的应用 Download PDFInfo
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- CN86104887A CN86104887A CN198686104887A CN86104887A CN86104887A CN 86104887 A CN86104887 A CN 86104887A CN 198686104887 A CN198686104887 A CN 198686104887A CN 86104887 A CN86104887 A CN 86104887A CN 86104887 A CN86104887 A CN 86104887A
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- Prior art keywords
- chloro
- phenoxy
- fluoropyridin
- yloxy
- propargyl
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- BGRYSGVIVVUJHH-UHFFFAOYSA-N prop-2-ynyl propanoate Chemical compound CCC(=O)OCC#C BGRYSGVIVVUJHH-UHFFFAOYSA-N 0.000 title claims description 16
- 239000004009 herbicide Substances 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title description 7
- 230000002363 herbicidal effect Effects 0.000 title description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title 1
- 229910052731 fluorine Inorganic materials 0.000 title 1
- 239000011737 fluorine Substances 0.000 title 1
- 229910052760 oxygen Inorganic materials 0.000 title 1
- 239000001301 oxygen Substances 0.000 title 1
- 241000196324 Embryophyta Species 0.000 claims abstract description 20
- JBDHZKLJNAIJNC-LLVKDONJSA-N clodinafop-propargyl Chemical compound C1=CC(O[C@H](C)C(=O)OCC#C)=CC=C1OC1=NC=C(Cl)C=C1F JBDHZKLJNAIJNC-LLVKDONJSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 24
- -1 propargyl ester Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 10
- PERMDYZFNQIKBL-UHFFFAOYSA-N 5-chloro-2,3-difluoropyridine Chemical compound FC1=CC(Cl)=CN=C1F PERMDYZFNQIKBL-UHFFFAOYSA-N 0.000 claims description 9
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- OLZPJUVEGSNIJL-UHFFFAOYSA-N 2,5-dichloropyridin-3-amine Chemical compound NC1=CC(Cl)=CN=C1Cl OLZPJUVEGSNIJL-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
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- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
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- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
本发明叙述了式1所示的(R)-2-[4-(5-氯-3-氟吡啶-2-基氧)苯氧基]丙酸炔丙基酯。
这个化合物适用于在栽培作物中选择性地防治杂草或降低杂草的生长。
Description
本发明涉及到新颖的（R）-2-〔4-（5-氯-3-氟吡啶-2-基氧）苯氧基〕丙酸炔丙基酯、它的生产、含该化合物作为有效成分的组合物，也涉及到作为除草剂的一般使用，和特别用于栽培作物，如谷类作物水稻、玉米、大豆，和甜菜中防治杂草。
（R）-2-〔4-（5-氯-3-氟吡啶-2-基氧）-苯氧基〕丙酸炔丙基酯可用式1表示，
（R）-2-〔4-（5-氯-3-氟吡啶-2-基氧）苯氧基〕丙酸炔丙基酯的特点是防治单子叶和某些双子叶杂草的效果很好。在出芽后处理中，它对不受欢迎的杂草和出现在栽培作物如玉米、水稻、大豆、和甜菜中的野生杂草是有效的。特别有价值的是，本发明的新颖化合物可用于防治难以防治的杂草，如野燕麦、Avena Sterilis、鼠尾看麦娘、黑麦草、Phalaris sp、旱雀麦、和狗尾草属与黍属的各种杂草。在田间条件下，甚至用药量低于每公顷一公斤，便可防治杂草。在此种剂量下，对栽培的作物是无伤害的，或者是仅有微不足道的伤害。
卤代吡啶基氧-α-苯氧基-丙酸衍生物在很多出版物（例如，联邦德国专利申请公开说明书Nos.2，546，251，2，649，706、2，714，622和2，715，284;欧洲专利公布Nos.483、1473、83556和97460）中已有记载。本发明的酯以其较好的除草作用不同于已知的囟代吡啶基氧-α-苯氧基丙酸类化合物。本发明的酯使用量范围较宽，例如，每公顷使用的有效成份在0.01到2公斤之间。
通式Ⅰ所示新颖的酯可以用式Ⅱ所示的5-氯-2，3-二氟吡啶在惰性溶剂或稀释剂中，在等克分子量的碱存在下，与式Ⅲ所示的（R）-2（4-羟基苯氧基）-丙酸炔丙基酯对映异构体作用来生产。
第二个生产方法是用式Ⅳ所示的4-（5-氯-3-氟吡啶-2-基氧）-苯酚在惰性溶剂或稀释剂中、在等克分子量碱存在下，与式Ⅴ所示的α-囟代丙酸炔丙基酯的（S）对映异构体反应。
式中Hal为囟原子
第三种生产方法是以式Ⅵ所示的2-[4-（5-氯-3-氟吡啶-2-基氧）苯氧基]丙酰囟（R）对映异构体，在惰性溶剂或稀释剂中和在等克分子量碱存在下，与炔丙醇HOCH2-C≡CH作用。
式中Hal为囟原子
另外，式Ⅰ所示的酯也可以用式Ⅶ所示的2-〔4-（5-氯-3-氟吡啶-2-基氧）苯氧基〕丙酸（R）对映异构体，在惰性溶剂或稀释剂中和在等克分子量碱存在下，与式Ⅷ所示的卤代丙炔反应来生产。
式中Hal为卤原子
最后，还有一个方法是式Ⅸ所示的2-〔4-（3-氨基-5-氯-吡啶-2-基氧）苯氧基〕丙酸炔丙基酯的（R）对映体，用已知的方法转化为重氮盐，再将重氮盐转化为氟化物。
式Ⅰ所示的酯的（R）一对映异构体还可以用式Ⅳ所示的4-（5-氯-3-氟吡啶-2-基氧）苯酚与式Ⅹ所示的（S）-乳酸炔丙基酯-磺酸酯，在惰性溶剂中和在碱存在下反应，并从反应混合物中分离出（R）-2-[4-（3-氟-5-氯吡啶-2-基氧）苯氧基]丙酸炔丙基酯。
在式Ⅹ中R为一个C1-C6烷基，它们可以是直链的、或支链的、可以是无取代基的、也可以是囟素、氰基、C1-C4烷氧羰基取代的烷基或者是一个苯基，此苯基可以是未取代的，也可以是C1-C4烷基、C1-C4烷氧基、囟素、硝基、氰基或C1-C4烷氧基羰基取代的苯基。
式Ⅱ所示的原料5-氯-2，3-二氟吡啶可以在氟化铯存在下，氟化相应的2，3，5-三氟吡啶来制备。产物可以从反应物中蒸馏出，但必须经分馏纯化。采取下述方法来制备5-氯-2，3-二氟吡啶也是可能的，即在例如阮内镍催化剂存在下，用氢将2，5-二氯-3-硝基吡啶氢化还原为3-氨基-2，5-二氯吡啶。然后，在氢氟酸存在下，用亚硝酸钠将后者转化为2，5-二氯-3-氟吡啶。再用氟化钾将生成物氟化成收率很好的2，3-二氟-5-氯吡啶。
式Ⅳ所示的原料4-（5-氯-3-氟吡啶-2-基氧）苯酚，可以通过5-氯-2，3-二氟吡啶与氢醌在碱存在下、在惰性有机溶剂中缩合来得到。
式Ⅸ所示的原料，可以通过，例如还原相应的（R）-2-[4-（5-氯-3-硝基吡啶-2-氧基）苯氧基]丙酸炔丙基酯来得到。
其它原料或为已知、或为易于用传统方法制得的。
这些反应中的许多反应可以很方便地在对反应物为惰性的有机溶剂或稀释剂中进行，例如醇、酯、醚、酮、二甲基甲酰胺、二甲基亚砜、乙腈、1，1-二氧-四氢噻吩、或芳香族化合物，如甲苯和二甲苯。
反应温度是在-10到150℃之间，不过，在实际操作中可以在室温和溶剂的沸点之间。反应时间取决于所选择的原料、溶剂和反应温度、约为1小时直到1天之间。
在有囟原子脱下来的反应中，应该使用等克分子量的酸结合剂。适合用作酸结合剂的基本上为无机碱或有机碱、如氢氧化钠、氢氧化钾、碳酸氢钠、碳酸钾、叔丁醇钾、和胺类，如三甲胺、三乙胺、吡啶、4-二甲氨基吡啶等等。
式I所示的新颖的活性物质是稳定的化合物，它可溶于常用的有机溶剂，如醇、醚、酮、二甲基甲酰胺、二甲基亚砜、及其它类似物中。
式I所示的化合物可以以单一化合物形式使用，但最好是与农药加工中常用的助剂合用。可以用熟知的办法将它加工成例如浓乳剂，能直接喷用或稀释后再用的溶液、乳油、可湿性粉剂、可溶性粉剂、粉剂或颗粒剂，也可以将药剂包在高分子材料中作成胶囊剂。其应用方法、如喷雾、气雾、撒粉、撒布、或浇灌。制剂的型式，应根据防治的目的和特定的条件来选择。
制剂加工、亦即配制含有式Ⅰ的活性物质和任选的固体或液体添加剂的组合物或制剂，是以熟知的方法进行的，例如，将活性物质与添加剂，如溶剂、固体载体和任选的表面活性剂密切混合和/或研磨。
适用的溶剂有：芳香烃，最好是C8-C12的馏份，如混合二甲苯或取代萘;邻苯二甲酸酯，如邻苯二甲酸二丁酯或二辛酯;脂肪烃，如环己烷、或链烷烃;醇类和二元醇类以及它们的酯和醚，如乙醇、乙二醇、乙二醇单甲醚或单乙醚;酮类如环己酮;强极性溶剂，如N-甲基-2-吡咯烷酮、二甲基亚砜或二甲基甲酰胺，以及任选的环氧化植物油，如环氧化椰子油或豆油;或者是水。
使用的固体载体，例如供粉剂或可分散粉末用的载体，通常是天然的矿物填料，如方解石、活石、高岭土、蒙脱土、或绿坡缕石（attapulgite）。为了改善制剂的物理性质，可以加入高度分散的硅酸或高度分散的有吸收性能的高分子物质。适用于颗粒的吸附性载体为多孔型的物质，如浮石、研碎砖头、海泡石、或膨润土;而合适的非吸附性载体为方解石、和砂子一类的物质。许多予先制成颗粒的无机或有机天然物，如特别是白云石、或粉碎的植物残渣也是可以应用的。
根据要配制的式Ⅰ所示活物质的性质，适用的表面活性剂为具有良好乳化、分散和可湿性能的非离子型的、阳离子型的和/或阴离子型的表面活性剂，也可以用混合的表面活性剂。适用的阴离子表面活性剂有所谓水溶性肥皂，以及水溶性的、合成的表面活性化合物。
可以采用的肥皂有：如（C10-C20的）高级脂肪酸的碱金属盐、碱土金属盐，或任意取代的铵盐、如油酸或硬脂酸的钾盐或钠盐，或者天然混合脂肪酸的钾盐或钠盐。此种天然混合脂肪酸可以从，例如椰子油或牛油中得到。还值得提出来的肥皂为脂肪酸-甲基-牛磺酸的各种盐。
所谓合成的表面活性剂是经常使用的、尤其是脂肪族磺酸盐、脂肪族硫酸盐、磺化过的苯并咪唑衍生物、或烷基芳基磺酸盐。脂肪族磺酸盐或硫酸盐通常是碱金属盐、碱土金属盐、或任意取代的铵盐，和分子中有一个8-22个碳原子的烷基的化合物，这里的“烷基”也包括酰基基团的烷基部分。例如，木质素磺酸的钠盐或钙盐、十二烷基硫酸酯的钠盐或钙盐、或者是天然脂肪酸得到的脂肪醇硫酸酯钠盐或钙盐混合物。脂肪醇氧化乙烯加成物的硫酸酯的盐和磺酸盐亦包括在其中。在磺化苯并咪唑衍生物中最好含有二个磺酸基团和一个有8-22个碳原子的脂肪酸基团。烷基芳基磺酸盐为，例如，十二烷基苯磺酸的、二丁基萘酸的、或萘磺酸缩合产物的钠盐、钙盐或三乙醇胺盐。相应的磷酸盐，如对-壬基苯酚-（4-14个）氧化乙烯加成物的磷酸酯也是适用的。
适合的非离子型表面活性剂是脂肪族或脂环族醇的、饱和或不饱和脂肪酸的、和烷基酚的聚二醇醚。这种醚的分子中可以拥有3-30个二醇醚基团，在（脂肪族）烃基中拥有8-20个碳原子，和烷基酚的烷基中拥有6-18个碳原子。
适用的非离子型表面活性剂还有水溶性的聚氧化乙烯与聚丙二醇、乙二氨基聚丙二醇、或与烷基链中含有1-10个碳原子的烷基聚丙二醇的加合物。此种加合物分子中含20-250个乙二醇醚基团和10-100个丙二醇醚基团。所提及的化合物分子中通常每有1个丙二醇单位就有1-5个乙二醇单位。可以提出来的非离子型表面活性剂的例子为：壬基苯酚-聚乙氧基乙醇，蓖麻油聚二醇醚、聚丙烯/聚乙撑氧加成物、三丁基苯氧-聚乙氧基乙醇、聚乙二醇和辛基苯氧-聚乙氧基乙醇。聚氧乙撑山梨糖醇酐的脂肪酸酯，如聚氧乙撑山梨糖醇酐-三油酸酯也是适合使用的。
就阳离子表面活性剂来说，它们特别是季铵盐，其分子中的N-取代基至少有一个有8-22个碳原子的烷基，其它的取代基为较小的烷基、任选的囟代烷基、苄基、或者是低级羟基烷基基团。特别可取的盐为囟化物、甲基硫酸盐、或乙基硫酸盐，例如硬脂基三甲基氯化铵、或苄基二（2-氯乙基）乙基溴化铵。
在制剂中常用的表面活性剂，特别记载于下述著作中：
“Mc cutcheon的去污剂和乳化剂手册”
Mc Publishing Corp.，Ridgewood，New Jersey，1979.
Sisely与Wood的“表面活性剂百科全书”
Chemical Publeshing Co.，Inc.New York，1964.
各种制剂一般含有0.1-99%，最好是0.1-95%式1所示的活性物质;1-99%的固体或液体添加剂;和0-25%，最好是0.1-25%的表面活性剂。
商业产品最可取的是高浓度组合物，通常由使用者稀释此种高浓度组合物。
组合物中也可以含有其它的添加剂，如稳定剂、去泡剂、粘度调节剂、粘结剂、和附着剂。组合物中也可加入肥料，或其它活性成份以达到某种特定的效果。
在下面的实例中详细地描述了（R）-2-[4-（5-氯-3-氟吡啶-2-基氧）-苯氧基]丙酸炔丙基酯的产生方法、和含有这些酯作为有效成份的组合物。各组分的百分比为重量百分比。
实例1（R）-2-[4-（5-氯-3-氟吡啶-2-基氧）苯氧基]丙酸炔丙基酯的制备
在搅拌及10℃下，将24.2克（0.11克分子）（R）-2-（4-羟基苯氧基）丙酸炔丙基酯与80毫升二甲基甲酰胺组成的溶液滴加到4.9克（0.11克分子）氢化钠（55%的分散剂）与30毫升二甲基甲酰胺的悬液中。加毕，继续在10℃下搅拌1小时。然后，向反应物中再滴加16.4克（0.10克分子）5-氯-2，3-二氟吡啶与40毫升二甲基甲酰胺组成的溶液，约4小时加毕，再在室温下搅拌24小时。将反应混合物倒入冰-水中，用乙醚提取三次。收集乙醚层，用水洗，浓氯化钠溶液洗、硫酸镁干燥，在硅胶上过滤。然后，浓缩乙醚溶液，得到的油状物在乙醇中结晶，给出25克（收率72%）所期望的丙炔基酯，m.p.55-56℃。用作原料的5-氯-2，3-二氟吡啶是用下述方法得到的。
a）3-氨基-2，5-二氯吡啶
将予先用乙醇洗过的阮内镍26.0克加到129.2克（0.69克分子）2，5-二氯-3-硝基吡啶及1300毫升二氧六环的溶液中。在常压及25-35℃下，用氢氢化上述混合物。当20%理论用量的氢被吸收之后，再加入30克洗过的阮内镍。氢化24小时后，滤掉催化剂，蒸去溶剂，残留物在己烷-乙酸乙酯中结晶，得到84.9克3-氨基-2，5-二氯吡啶（收率78%），m.p.129-132℃。
b）2，5-二氯-3-氟吡啶
将163克（1.0克分子）3-氨基-2，5-二氯吡啶，在-5--1℃下加到450毫升（22.5克分子）装在不锈钢反应器中的氟化氢中去，然后在上述温度及搅拌下，加入82.8克（1.2克分子）亚硝酸钠。反应混合物在-5--1℃下搅拌1.5小时，然后使温度慢慢地上升到60℃。在气体停止释放之后，蒸掉氟化氢，残留物用二氯甲烷处理，再加入冰-水。冷却的混合物用浓氢氧化铵溶液中和。分出有机层，水层用二氯甲烷提取三次。有机相用水洗、硫酸镁干燥、通过硅胶过滤，然后蒸发，得到141.5克（收率85%）2，5-二氯-3-氟吡啶。
c）5-氯-2，3-二氟吡啶
将64.6克（1.1克分子）氟化钾，11.25（0.075克分子）氟化铯及240毫升1，1-二氧代-四氢噻吩的悬浮液加热到140℃。减压蒸出50毫升1，1-二氧代-四氢噻吩，向残留的悬浮液中加入61.4克（0.37克分子）2，5-二氯-3-氟吡啶及20毫升1，1-二氧代-四氢噻吩的溶液。反应混合物在140℃下搅拌35小时，冷却，然后倒入冰-水中。用乙醚提取有机物，乙醚层经水洗、硫酸镁干燥、过滤、并蒸发，便得到48.7克无色油状液体（收率88%），沸点55-66℃/133毫巴。
实例2
（R）（+）-2-[4-（5-氯-3-氟吡啶-2-基氧）苯氧基]丙酸炔丙基酯的制备
在冰浴冷却和搅拌下，将10.6克（0.030克分子）（R）（+）-2-[4-（5-氯-3-氟吡啶-2-基氧）苯氧基]丙酰氯及100毫升甲苯的溶液慢慢地加到4.9毫升（0.035克分子）三乙胺和2毫升（0.035克分子）炔丙醇及40毫升甲苯的溶液中，加毕，移走冰浴，反应混合物在室温下搅拌3小时。将反应混合物倒入冰-水中，用乙酸乙酯提取有机物两次。乙酸乙酯层用饱和盐溶液洗涤、经硫酸镁干燥、过滤并蒸发。残留物用硅胶柱层析纯化，以己烷-乙酸乙酯溶液作洗提剂。蒸掉溶剂后，残留物便出现结晶，m.p.54℃（[α]20 D＝+45.4°，2%，丙酮）
用作原料的（R）（+）-2-[4-（5-氯-3-氟吡啶-2-基氧）苯氧基]丙酰氯是用下述方法得到的。a）4-（5-氯-3-氟吡啶-2-基氧）苯酚
将27.5克（0.25克分子）氢醌、11.2克（0.2克分子）氢氧化钾、及600毫升二甲基亚砜的混合物在室温及氮气保护下搅拌，直到固体物完全溶解，然后滴加30克（0.2克分子）5-氯-2，3-二氟吡啶及200毫升二甲基亚砜的溶液。将反应混合物加热到70℃，并在70℃下搅拌4小时。然后倒入冰-水中，并用盐酸酸化、乙酸乙酯提取。乙酸乙酯层经硫酸镁干燥、过滤、蒸发至干。残留物用己烷-乙酸乙酯（2∶1）的溶剂处理，并通过硅胶柱纯化。洗提液经浓缩之后，残留物便结晶，生成33克白色结晶，m.p 97-98℃。
b）.（R）（+）-2-[4-（5-氯-3-氟吡啶-2-基氧）苯氧基]丙酸甲酯
将40克（0.1克分子）4-（5-氯-3-氟吡啶-2-基氧）苯酚及80毫升二甲基亚砜的溶液，在搅拌下，滴加到含13.8克（0.1克分子）碳酸钾的50毫升二甲基亚砜中，加毕，在室温下搅拌反应混合物2小时。然后滴加25.8克（0.1克分子）（S）（-）-乳酸甲酯的甲苯磺酸酯，约30分钟加毕。将反应混合物加热至60℃，并在此温度下搅拌20小时，然后倒入冰-水中。用乙醚提取有机物三次。乙醚层经水洗、饱和盐水洗、硫酸镁干燥、过滤、和蒸发。残留物通过硅胶柱纯化，用3∶1的己烷-乙酸乙酯作溶剂。蒸掉溶剂之后，得到26g克清亮的所需的酯（[α]20 D＝+38.8±0.5°2%，丙酮）
c）（R）（+）-2-[4-（5-氯-3-氟吡啶-2-基氧）苯氧基]丙酸
于13.0克（0.04克分子）（R）（+）-2-[4-（5-氯-3-氟吡啶-2-基氧）苯氧基]-丙酸甲酯及65毫升二氧六环的溶液中，加入42毫升1N的氢氧化钠溶液。混合物在35℃下搅拌2.5小时，然后倒入冰-水中，并用22毫升2N盐酸酸化。用乙酸乙酯提取有机物二次。有机层用饱和盐水洗涤、硫酸镁干燥、过滤、和浓缩，残留物在乙酸乙酯-己烷中结晶，得到10.2克（收率81.8%）（R）（+）-2-[4-（5-氯-3-氟吡啶-2-基氧）苯氧基]丙酸，白色结晶、m.p.95-96℃（[α]20 D＝+37.5±0.5，2%，丙酮）
d）（R）（+）-2-[4-（5-氯-3-氟吡啶-2-基氧）苯氧基]丙酰氯
将10.8克（0.035克分子）（R）（+）-2-[4-（5-氯-3-氟吡啶-2-基氧）苯氧基]丙酸溶于150毫升甲苯中，然后在加热至130℃的油浴中蒸出50毫升甲苯。将反应混合物冷却到90℃，慢慢地加入3.8毫升亚硫酰氯。混合物在90℃下搅拌16小时，并在减压下蒸发，残留物结晶，m.p.47-48℃。
实例3用式Ⅰ所示的液体活性组分生产制剂（%为重量百分率）
浓乳剂 a） b） c）
（R）-2-[4-（5-氯-3-氟吡啶-2-基氧）
苯氧基]丙酸炔丙基酯 20% 40% 50%
十二烷基苯磺酸钙 5% 8% 5.8%
蓖麻油-聚乙二醇醚（36个环氧乙烷分子） 5% - -
三丁基酚-聚乙二醇醚（30个环氧乙烷分子） - 12% 4.2%
环己酮 - 15% 20%
混合二甲苯 70% 25% 20%
用水稀释浓乳剂可以生成所需各种浓度的乳剂。
溶液 a） b） c） d）
（R）-2-[4-（5-氯-3-氟吡啶-2-基氧）
苯氧基]丙酸炔丙基酯 80% 10% 5% 95%
乙二醇-单甲醚 20% - - -
聚乙二醇MG400 - 70% - -
N-甲基-2-吡咯烷酮 - 20% - -
环氧化椰子油 - - 10% 5%
石油醚（沸点范围160-190℃） - - 94% -
此溶液适合于以非常细的雾滴形式使用
粒剂 a） b）
（R）-2-[4-（5-氯-3-吡啶-2-基氧）
苯氧基]丙酸炔丙基酯 5% 10%
高岭土 94% -
高度分散的硅酸 1% -
绿坡缕石 - 90%
活性成份溶解在二氯甲烷中，然后喷在载体上，再在真空下蒸掉溶剂。
粉剂 a） b）
（R）-2-[4-（5-氯-3-氟吡啶-2-基氧）
苯氧基]丙酸炔丙基酯 2% 5%
高度分散的硅酸 1% 5%
滑石 97% -
高岭土 - 90%
通过密混合载体与活性成份来得到随时可用的粉剂。
式Ⅰ所示的固体活性组份配成制剂的实例（%为重量百分率）
可湿性粉剂 a） b）
（R）-2-[4-（5-氯-3-氟吡啶-2-基氧）
苯氧基]丙酸炔丙基酯 20% 60%
木质素磺酸钠 5% 5%
十二烷基硫酸钠 3% -
二丁基萘磺酸钠 - 6%
辛基苯酚-聚乙二醇醚（7-8个环氧乙烷分子）- 2%
高度分散的硅酸 5% 27%
高岭土 67% -
将活性成份与各种添加剂混匀，然后用适合的粉碎机研磨。可湿性粉剂可用水稀释来得到所需浓度的悬浮液。
浓乳剂
（R）-2-[4-（5-氯-3-氟吡啶-2-基氧）
苯氧基]丙酸炔丙基酯 10%
辛基苯酚-聚乙二醇醚（4-5个环氧乙烷分子） 3%
十二烷基苯磺酸钙 3%
蓖麻油聚乙二醇醚（36个环氧乙烷分子） 4%
环己酮 30%
混合二甲苯 50%
用水稀释这种浓乳剂能得到所需浓度的乳剂。
粉剂 a）% b）%
（R）-2-[4-（5-氯-3-氟吡啶-2-基氧）
苯氧基]丙酸炔丙基酯 5% 8%
滑石粉 95% -
高岭土 - 92%
在适当的研磨机中将活性成份与各种载体的混合物研磨得到随时可用的粉剂。
挤压粒剂
（R）-2-[4-（5-氯-3-氟吡啶-2-基氧）
苯氧基]丙酸炔丙基酯 10%
本质素磺酸钠 2%
羧甲基纤维素 1%
高岭土 87%
活性成份与各种添加剂混合并研磨。将混合物用水湿润并挤压成粒，然后在空气流中干燥。
涂表粒剂
（R）-2-[4-（5-氯-3-氟吡啶-2-基氧）
苯氧基]丙酸炔丙基酯 3%
聚乙二醇 MG 200 3%
高岭土 94%
在混合器中将研细的活性成份均匀地施于用聚乙二醇湿润过的高岭土上，这样便得到无粉尘的涂表粒剂。
浓悬剂
（R）-2-[4-（5-氯-3-氟吡啶-2-基氧）
苯氧基]丙酸炔丙基酯 40%
乙二醇 10%
壬基苯酚聚乙二醇醚（15个环氧乙烷分子） 6%
木质素磺酸钠 10%
羧甲基纤维素 1%
37%甲醛水溶液 0.2%
75%水乳剂形式的硅油 0.8%
水 32%
将研细的活性成份与各种添加剂混匀即得到浓悬剂。用水稀释浓悬剂便得到各种所需浓度的悬浮液。
实例4 除草作用
芽后除草作用（接触除草剂）
在温度中，将玉蜀黍、杂交高梁、稻子、野燕麦、旱雀麦、黑麦草、鼠尾看麦娘、马唐、稗草、约翰逊草、和简竹茅种在盆中。在出芽后（4-6叶期），用不同剂量待测试化合物的水悬浮液喷植株。剂量用（有效成份）克/公顷表示。处理后的植株保持在24-26℃及45-60%相对湿度的条件下，并定期浇水。10天后评估试验的结果。
植物的状况按照下述的伤害等级进行评估：
9：无伤害，植株生长得与未处理的植株一样。
1.完全受伤害，植株死亡
2-8：受伤害的程度介于1-9之间
试验评价了每种用药量对每种杂草的伤害等级，而在附图1中采用了对所有试验植物伤害等级的平均值。
在这个图中，采用测试物质对各种杂草活性的平均值对每种使用药量作图。为了达到相当于良好杀草活性标志的3级水平，外消旋体需要86克的用量，令人惊奇的是，为达到相同的活性水平，（R）-对映异构体只要42克的用量。（R）-对映异构体对这些杂草的活性要比外消旋体大一倍多。
Claims (5)
1、式Ⅰ所示的(R)-2-[4-(5-氯-3-氟吡啶-2-基氧)苯氧基]丙酸炔丙基酯。
2、含有有效量权利要求1的（R）-2-〔4-（5-氯-3-氟吡啶-2-基氧）苯氧基〕丙酸炔丙基酯及惰性载体的除草的和调节植物生长的组合物。
3、一种选择性防治杂草的方法，其特征是，施用除草有效量的权利要求1的（R）-2-〔4-（5-氯-3-氟吡啶-2-基氧）苯氧基〕丙酸炔丙基酯。
4、一种生产权利要求1的（R）-2-〔4-（5-氯-3-氟吡啶-2-基氧）苯氧基〕丙酸炔丙基酯对映异构体的方法，其特征是该方法包括式Ⅱ所示的5-氯-2，3-二氟吡啶，在惰性溶剂或稀释剂中和在等克分子量的碱存在下，与式Ⅲ所示的所示的（R）-2-（4-羟基-苯氧基）-丙酸炔丙基酯对映异构体反应。
5、一种生产权利要求1的（R）-2-〔4-（5-氯-3-氟吡啶-2-基氧）苯氧基〕丙酸炔丙基酯对映异构体的方法，其特征是该方法包括式Ⅵ所示的（R）-2-〔4-（5-氯-3-氟吡啶-2-基氧）苯氧基〕丙酰卤对映异构体，在惰性溶剂或稀释剂中和在等克分子量的碱存在下，与炔丙醇（HO-CH2-C≡CH）反应，
式中Hal为卤素。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2376/86-3 | 1986-06-12 | ||
| CH2376/86A CH679396A5 (zh) | 1986-06-12 | 1986-06-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN86104887A true CN86104887A (zh) | 1987-12-23 |
Family
ID=4232328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198686104887A Pending CN86104887A (zh) | 1986-06-12 | 1986-08-05 | (r)-2-[4-(5-氯-3-氟吡啶-2-基氧)苯氧基]丙酸炔丙基酯的制备方法及其作为除草剂的应用 |
Country Status (30)
| Country | Link |
|---|---|
| EP (1) | EP0248968A1 (zh) |
| JP (1) | JPS62292758A (zh) |
| KR (1) | KR910000601B1 (zh) |
| CN (1) | CN86104887A (zh) |
| AU (1) | AU592804B2 (zh) |
| BR (1) | BR8603381A (zh) |
| CA (1) | CA1236106A (zh) |
| CH (1) | CH679396A5 (zh) |
| CS (1) | CS261243B2 (zh) |
| DD (2) | DD272069A5 (zh) |
| DK (1) | DK162216C (zh) |
| EG (1) | EG18260A (zh) |
| ES (2) | ES2000663A6 (zh) |
| FI (1) | FI87772C (zh) |
| GR (1) | GR861757B (zh) |
| HU (1) | HU206243B (zh) |
| IL (1) | IL79330A0 (zh) |
| MX (2) | MX3121A (zh) |
| MY (1) | MY102085A (zh) |
| NO (1) | NO168528C (zh) |
| NZ (1) | NZ216736A (zh) |
| PH (1) | PH21693A (zh) |
| PL (1) | PL147477B1 (zh) |
| PT (1) | PT82937B (zh) |
| SU (1) | SU1567116A3 (zh) |
| TN (1) | TNSN86112A1 (zh) |
| TR (1) | TR22984A (zh) |
| YU (2) | YU44582B (zh) |
| ZA (1) | ZA864947B (zh) |
| ZW (1) | ZW12486A1 (zh) |
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|---|---|---|---|---|
| CN100467452C (zh) * | 2006-11-01 | 2009-03-11 | 浙江工业大学 | 一种制备具有高光学纯度精吡氟氯禾灵的方法 |
| CN102907430A (zh) * | 2012-11-19 | 2013-02-06 | 江苏扬农化工股份有限公司 | 一种含麦草畏和炔草酯的除草组合物及其应用 |
| CN101016237B (zh) * | 2006-02-10 | 2013-10-23 | 上海生农生化制品有限公司 | 一种r(+)-2-(4-羟基苯氧基)-丙酸的合成方法 |
| CN105418494A (zh) * | 2015-12-15 | 2016-03-23 | 南京正荣医药化学有限公司 | 一种炔草酯的制备方法 |
| CN105494347A (zh) * | 2016-02-23 | 2016-04-20 | 陕西上格之路生物科学有限公司 | 一种含三甲苯草酮和炔草酯的除草组合物 |
| CN105519534A (zh) * | 2014-09-28 | 2016-04-27 | 南京华洲药业有限公司 | 一种含炔草酯与吡草醚的复合除草组合物及其应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE59008552D1 (de) * | 1989-01-11 | 1995-04-06 | Ciba Geigy Ag | Antidots zur Verbesserung der Kulturpflanzenvertäglichkeit agrochemischer Wirkstoffe. |
| US5258521A (en) * | 1989-07-26 | 1993-11-02 | Tosoh Corporation | Process of producing optically active propionic acid ester derivatives |
| US5274100A (en) * | 1990-10-23 | 1993-12-28 | Ciba-Geigy Corporation | Process for the preparation of (3-fluoropyridin-2-yloxy)phenoxypropionic acids |
| RO117587B1 (ro) * | 1991-07-12 | 2002-05-30 | Hoechst Ag | Compozitie erbicida, procedeu de obtinere a acesteia si metoda pentru controlul plantelor nedorite |
| SK322292A3 (en) * | 1991-11-15 | 1995-12-06 | Ciba Geigy Ag | Synergic agent and method of selective weed suppression |
| DE4318092C1 (de) * | 1993-06-01 | 1995-01-12 | Basf Ag | Verfahren zur Herstellung von (R)- oder (S)-2-(4-Alkanoylphenoxy)- und (R)- oder (S)-2-(4-Aroylphenoxy)-propionsäureestern |
| US5650517A (en) * | 1994-11-01 | 1997-07-22 | Ciba-Geigy Corporation | Process for the preparation of 2,3-difluoro-5-halopyridines |
| US5985797A (en) * | 1996-07-17 | 1999-11-16 | Bayer Aktiengesellschaft | Herbicidal compositions based on N-isopropyl-N-(4-fluorophenyl) (5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy)acetamide |
| DE19728568B4 (de) * | 1996-07-17 | 2007-06-14 | Bayer Cropscience Ag | Herbizide Mittel auf Basis von (5-Trifluormethyl-1,3,4-thiadiazol-2-yl-oxy)-essigsäure-N-isopropyl-N-(4fluorphenyl)-amid |
| AU719087B2 (en) | 1998-03-24 | 2000-05-04 | Syngenta Participations Ag | Process for preparation of propionic acid derivatives |
| AR032844A1 (es) * | 2001-02-26 | 2003-11-26 | Syngenta Participations Ag | Composicion herbicida |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH650493A5 (en) * | 1977-12-24 | 1985-07-31 | Hoechst Ag | D-(+)-alpha-phenoxypropionic acid derivatives |
| DE2963229D1 (en) * | 1978-06-29 | 1982-08-19 | Ciba Geigy Ag | Herbicidal, optically active r(+)-dichloropyridyloxy-alpha-phenoxy-propionic acid-propargylesters, process for their preparation and their use in herbicidal compositions |
| US4505743A (en) * | 1981-12-31 | 1985-03-19 | Ciba-Geigy Corporation | α-[4-(3-Fluoro-5'-halopyridyl-2'-oxy)-phenoxy]-propionic acid derivatives having herbicidal activity |
| CA1215924A (en) * | 1983-07-27 | 1986-12-30 | David W. Bewick | Process for producing optically active aryloxypropionic acids and derivatives thereof useful as herbicides |
| DE3403974A1 (de) * | 1984-02-04 | 1985-08-14 | Bayer Ag, 5090 Leverkusen | Optisch aktive phenoxypropionsaeure-derivate |
| DE3680212D1 (de) * | 1985-02-14 | 1991-08-22 | Ciba Geigy Ag | Verwendung von chinolinderivaten zum schuetzen von kulturpflanzen. |
-
1986
- 1986-06-12 CH CH2376/86A patent/CH679396A5/de not_active IP Right Cessation
- 1986-06-27 DK DK307186A patent/DK162216C/da not_active IP Right Cessation
- 1986-06-30 FI FI862769A patent/FI87772C/fi not_active IP Right Cessation
- 1986-07-01 NO NO862665A patent/NO168528C/no unknown
- 1986-07-02 AU AU59491/86A patent/AU592804B2/en not_active Expired
- 1986-07-02 DD DD86312694A patent/DD272069A5/de not_active IP Right Cessation
- 1986-07-02 DD DD86292079A patent/DD253754A5/de not_active IP Right Cessation
- 1986-07-02 NZ NZ216736A patent/NZ216736A/xx unknown
- 1986-07-02 YU YU1170/86A patent/YU44582B/xx unknown
- 1986-07-03 ZW ZW124/86A patent/ZW12486A1/xx unknown
- 1986-07-03 CS CS865038A patent/CS261243B2/cs unknown
- 1986-07-03 ZA ZA864947A patent/ZA864947B/xx unknown
- 1986-07-03 IL IL79330A patent/IL79330A0/xx not_active IP Right Cessation
- 1986-07-07 HU HU862832A patent/HU206243B/hu not_active IP Right Cessation
- 1986-07-07 EP EP86810300A patent/EP0248968A1/de not_active Withdrawn
- 1986-07-07 GR GR861757A patent/GR861757B/el unknown
- 1986-07-08 PT PT82937A patent/PT82937B/pt unknown
- 1986-07-08 CA CA000513270A patent/CA1236106A/en not_active Expired
- 1986-07-11 PH PH34005A patent/PH21693A/en unknown
- 1986-07-14 MX MX312186A patent/MX3121A/es unknown
- 1986-07-14 JP JP61165450A patent/JPS62292758A/ja active Granted
- 1986-07-14 ES ES8600276A patent/ES2000663A6/es not_active Expired
- 1986-07-14 PL PL1986260614A patent/PL147477B1/pl unknown
- 1986-07-15 TR TR391/86A patent/TR22984A/xx unknown
- 1986-07-17 BR BR8603381A patent/BR8603381A/pt unknown
- 1986-07-18 TN TNTNSN86112A patent/TNSN86112A1/fr unknown
- 1986-07-21 KR KR1019860005897A patent/KR910000601B1/ko not_active Expired
- 1986-07-31 SU SU864027879A patent/SU1567116A3/ru active
- 1986-08-05 CN CN198686104887A patent/CN86104887A/zh active Pending
- 1986-10-07 EG EG627/86A patent/EG18260A/xx active
-
1987
- 1987-02-05 ES ES8700267A patent/ES2007331A6/es not_active Expired
- 1987-09-29 MY MYPI87002264A patent/MY102085A/en unknown
- 1987-11-03 YU YU1996/87A patent/YU44644B/xx unknown
-
1991
- 1991-07-22 MX MX9100319A patent/MX9100319A/es unknown
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| CN100467452C (zh) * | 2006-11-01 | 2009-03-11 | 浙江工业大学 | 一种制备具有高光学纯度精吡氟氯禾灵的方法 |
| CN102907430A (zh) * | 2012-11-19 | 2013-02-06 | 江苏扬农化工股份有限公司 | 一种含麦草畏和炔草酯的除草组合物及其应用 |
| CN102907430B (zh) * | 2012-11-19 | 2015-01-07 | 江苏扬农化工股份有限公司 | 一种含麦草畏和炔草酯的除草组合物及其应用 |
| CN105519534A (zh) * | 2014-09-28 | 2016-04-27 | 南京华洲药业有限公司 | 一种含炔草酯与吡草醚的复合除草组合物及其应用 |
| CN105418494A (zh) * | 2015-12-15 | 2016-03-23 | 南京正荣医药化学有限公司 | 一种炔草酯的制备方法 |
| CN105418494B (zh) * | 2015-12-15 | 2018-06-05 | 南京正荣医药化学有限公司 | 一种炔草酯的制备方法 |
| CN105494347A (zh) * | 2016-02-23 | 2016-04-20 | 陕西上格之路生物科学有限公司 | 一种含三甲苯草酮和炔草酯的除草组合物 |
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