CN1190428C - 取代苯基噁唑烷酮类除草剂 - Google Patents
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Abstract
本发明合成了取代苯基噁唑烷酮类七只高效新结构除草剂，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-位的噁唑烷酮具有的生物活性外，改变了苯环上5-位取代基团，此变化不影响苯环与杂环之间的夹角及长度，使本发明得到的新化合物具有超高效、低毒等药效。
Description
本发明属于精细化工农药除草剂。
1992年，新化合物KPP-314被发现，其结构式为：
该化合物应用的作物为水稻。
近年来，日本科研制药公司、组合化学公司、法国拜耳公司、巴斯夫公司及美国杜邦等公司相继发表高效除草剂，如：ET-751，KIH-9201，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。
由于人类对环保问题的重视，对农药的毒性及对环境的影响，提出了更高的要求，因此，化学农药将进入“超高效、无毒、无污染”的新时期。
本发明的目的就是开发研制一种高效农药除草剂。
本发明为取代苯基噁唑烷酮类除草剂，苯环上的1-位与杂环相连，其结构上最大的特点在于：
1.苯环上5-位可分别由氢、硫代乙酸甲酯基、丙烯酸甲酯基取代，也可与苯环6-位形成苯并呋喃；
2.苯环上4-位由氢、三氟甲基、氯原子取代；3.2-位由氢、氟原子取代：
以上合成了七个新结构的高效除草剂，它们的结构为：
上述七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.脱色的除草作用；
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：
该反应可以分二步进行：
(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)，即：
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作催化剂。
(2)丙烯酸甲酯基苯胺的合成：
将2-氟-4-氯-5-氨基酰替苯胺与丙烯酸、亚硝酸叔丁酯在氯化铜催化剂存在下反应而制得，即：
原料酰替苯胺与丙烯酸甲酯的配比为1∶20，反应在氯化铜存在下，在乙腈中进行，得到的产品(B′)在碱性条件下，发生消除反应制得产品(C′)，然后在酸性条件下水解制得产品(D′)。
(3)硫代乙酸甲酯基酰替苯胺的合成：
2-氟-4-氯-5-氨基酰替苯胺经重氮化后，与巯基乙酸反应制得相应的巯基乙酸化合物，再经甲酯化及水解制得产品，即：
本反应分三步进行：
(a)氨基化合物(A′)和亚硝酸钠水溶液，在酸性条件下重氮化反应生成中间产物(B″)；
(b)重氮化合物在碱式碳酸铜存在下和巯基乙酸反应生成产物(C″)；
(c)产物(C″)经水解、酯化得到产品(D″)。
(4)噁唑烷酮的合成：
由相应的胺和固体光气反应生成异氰酸酯，然后在三乙胺催化下，与丁烯酸乙酯加成制得中间产物，再在无水乙酸钠存在下闭环得到产品，即：
其中R＝氢，硫代乙酸甲酯、丙烯酸甲酯、呋喃。
胺类化合物与固体光气的摩尔比为1∶2，胺类与丁烯酸乙酯的配比为1∶1.1，反应a的溶剂为乙酸乙酯，b反应在苯中进行，c反应在N，N-二甲基甲酰胺中进行。
由于噁唑烷酮类化合物以植物细胞的叶绿素为作用点，因此，确保动植物之间的选择毒性，具有高效、低毒。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。经盆栽实验，结果如下：
试验的植物：
稗草(Echinochloa crusgalli) 苘 麻(Abutilon thephrasti)
马唐(Digitaria sanguinolis) 苋 菜(Acalypha australis)
狗尾(Setaria viridis) 百日草(Zinnia elegans)
初筛结果：
I#剂量(133gai/亩)下，茎叶处理对苋菜和苘麻有效，对其它作用较差。
II#剂量(133gai/亩)下，茎叶处理对苘麻有效。
III#剂量(10gai/亩)下，茎叶处理和土壤处理均表现明显防效，进入下一步复筛。
IV#剂量(133gai/亩)下，茎叶处理对苘麻有较高的抑制作用，土壤处理在剂量(133gai/亩)抑制作用明显。
V#剂量(133gai/亩)下，对阔叶草的杀死作用十分明显，对禾本科草作用稍差。
VI#剂量(133gai/亩)下，作用十分明显，且试验过程中发现它的作用现象与III#十分相似，进入下一步复筛。
VII#剂量(133gai/亩)下，对苘麻有效。
VIII#为本公司2000年申请的中国专利化合物，其结构为：
复筛结果：
III#、VI#、VIII#三种药剂对阔叶草的活性均高于对禾本科草的活性，且茎叶处理的效果优于土壤处理的特点。推断可能的原因是：这三种药剂同是抑制原卟啉原氧化酶的作用，属于光和抑制剂，所以茎叶处理的效果好于土壤处理。III#推荐用量5gai/亩，茎叶处理；VI#推荐用量8gai/亩，茎叶处理；VIII#推荐用量8gai/亩，茎叶处理。
三种药剂不同用量茎叶处理对不同杂草的抑制率
| 序号 | 处理量 | 药效(抑制率) |
| 稗草 狗尾 马唐 苋菜 苘麻 百日草 | ||
| 1 | III#低量 | 50.9 54.9 89.2 92.5 89.7 76.7 |
| 2 | III#中量 | 56.2 61.9 87.4 95.8 89.3 78.5 |
| 3 | III#高量 | 69.3 86.6 87.6 94.8 89.9 82.3 |
| 4 | VI#低量 | 31.8 70.2 77.0 93.0 89.7 81.8 |
| 5 | VI#中量 | 62.0 91.8 87.2 95.8 90.1 81.4 |
| 6 | VI#高量 | 66.2 95.7 91.8 94.6 90.0 88.8 |
| 7 | VIII#低量 | 48.3 37.4 73.1 87.6 89.0 66.3 |
| 8 | VIII#中量 | 55.6 67.3 83.4 93.8 88.7 72.5 |
| 9 | VIII#高量 | 61.7 54.0 88.8 96.9 88.1 79.0 |
上表中的药剂及药量：低量：5g/亩；中量：8g/亩；高量：15g/亩；
实施例1
10.4克芳胺溶于20毫升N，N-二乙基苯胺中，回流12小时，冷却至室温后，溶于乙酸乙酯中，用10％盐酸洗三次，脱去二乙基苯胺后的反应液，经干燥及浓缩，用己烷∶乙酸乙酯＝4∶1柱层析提纯，得到产品7.4克，收率71％。
取上步产品4.8克溶于20毫升氯仿中，5℃滴加CF3SO3H4.6克，5分钟加完，然后在室温反应5小时，反应完全后，反应液倾入30毫升5％氢氧化钠溶液中，用乙酸乙酯萃取、干燥、浓缩，得苯并呋喃3.5克，收率：86％，产品经H-NMR确认结构。
实施例2
34.4克丙烯酸甲酯，6.2克亚硝酸叔丁酯在200毫升乙腈中，加氯化铜6.5克，搅拌下加8.1克料胺，室温反应1小时，加100毫升3摩尔/升的盐酸洗，乙酸乙酯萃取，有机层经水洗，饱和食盐水洗，用无水硫酸镁干燥，减压浓缩，在乙醇中重结晶得9.5克，收率77％，丙烯酸甲酯基苯胺经H-NMR确认结构。
实施例3
7.0克4-(N-甲酰氨基)-2-氨基-1-氯-5-氟苯悬浮于9毫升浓盐酸和40毫升水及60克冰的混合液中，在0～5℃，滴加2.5克亚硝酸钠和8毫升水配成的溶液，在此温度下反应1小时，制得的重氮化液，加入0.2克氨基磺酸，再加4.1克巯基乙酸和23克碱式碳酸铜及34毫升水溶液，在室温下反应30分钟。滴加8.4毫升50％氢氧化钠调节pH值为7～8，再在95～100℃反应1小时。反应液趁热过滤出铜盐，用浓盐酸12毫升将滤液酸化后，用乙酸乙酯萃取。萃取液经常规处理后，得到4.8克5-(N-甲酰氨基)-2-氯-4-氟苯基硫乙酸，收率50％，产品经H-NMR确认结果。
实施例4
在250毫升四口瓶中，放4克固体光气，80毫升乙酸乙酯，20分钟内滴加4.5克芳胺的乙酸乙酯液，滴加完后，回流反应2小时，减压浓缩得产品5.8克，含量75％，收率82.8％。取上步产物5.8克与3克丁烯酸乙酯在80毫升苯中，加0.5克触媒三乙胺，室温下反应0.5小时，反应完全后，用1摩尔/升盐酸洗，浓缩得黄色油。
取上面反应黄色油溶于150毫升N，N-二甲基甲酰胺中，加1.5克无水乙酸钠，在50℃反应5小时，反应结束后，加入150毫升1摩尔/升盐酸，用2×100毫升乙醚萃取水层，合并油层经酸洗、水洗、干燥、浓缩，得油状物3-(2-氟-4-氯-5-丙烯酸甲酯基-苯基)-5-异丙叉基噁唑烷-2，4二酮，经乙醇重结晶，得产品4.5克，收率65％(以芳胺为原料计算)，产品结构经H-NMR确认。
Claims (1)
1.一种取代苯基噁唑烷酮除草剂，其特征在于本除草剂的分子结构苯环上1位与噁唑杂环相连接，2、4位分别由氟原子和氯原子取代，5、6位连接呋喃或5位由丙烯酸甲酯基取代，得到三个除草剂(III)、(VI)、(VII)：
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