CN1043228C - 选择性卤化制备卤代苯氧基脂肪酸衍生物的方法和卤代苯氧基脂肪酸衍生物 - Google Patents

选择性卤化制备卤代苯氧基脂肪酸衍生物的方法和卤代苯氧基脂肪酸衍生物 Download PDF

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CN1043228C
CN1043228C CN93104506A CN93104506A CN1043228C CN 1043228 C CN1043228 C CN 1043228C CN 93104506 A CN93104506 A CN 93104506A CN 93104506 A CN93104506 A CN 93104506A CN 1043228 C CN1043228 C CN 1043228C
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日野智和
津幡健治
滨口洋
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Abstract

本发明提供了制备由式(Ⅰ)表示的卤代苯氧基脂肪酸衍生物的方法，包括，在卤化剂存在下，选择性卤化由下述式(Ⅱ)表示的苯氧基脂肪酸，本发明进一步提供了由式(I′)表示的新的卤代苯氧基脂肪酸衍生物，由本发明的方法所得到的卤代苯氧基脂肪酸衍生物用作除草剂和其他物质的中间体。

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选择性卤化制备卤代苯氧基脂肪酸衍生 物的方法和卤代苯氧基脂肪酸衍生物
本发明涉及制备由下式(Ⅰ)表示的卤代苯氧基脂肪酸衍生物的方法，
Figure C9310450600051
[式中R代表氰基，-CON(R3)R4(其中R3和R4可相同或不同，每个代表氢原子、低级烷基、苯基、具有相同或不同的1至5个取代基的苯基，其取代基选自卤原子、硝基、氰基、低级烷基、低级卤代烷基、低级烷氧基、低级卤代烷氧基、低级烷基硫代基和低级卤代烷基硫代基，苄基或具有相同或不同的1至5个取代基的苄基，其取代基选自低级烷基、低级卤代烷基、低级烷氧基、低级卤代烷氧基、低级烷基硫代基和低级卤代烷基硫代基，并且R3和R4可一起代表亚烷基)或COAR5(其中R5代表氢原子，低级烷基，苯基，具有相同或不同的1至5个取代基的苯基，其取代基选自卤原子、硝基、氰基、低级烷基、低级卤代烷基、低级烷氧基、低级卤代烷氧基、低级烷基硫代基和低级卤代烷基硫代基，苄基或具有相同或不同的1至5个取代基的苄基，其取代基选自低级烷基、低级卤代烷基、低级烷氧基、低级卤代烷氧基、低级烷基硫代基和低级卤代烷基硫代基，和A代表氧原子或硫原子)，R1和R2可相同或不同，每个代表氢原子或低级烷基，X代表卤原子或低级烷基和Y代表卤原子]以及进一步涉及由所说的方法得到的部分卤代苯氧基脂肪酸衍生物。
在本说明书中术语“低级”烷基或类似的基团指的是具有1至6个碳原子的基团。
通常，卤代苯氧基脂肪酸衍生物的制备是通过卤化一卤代苯酚得到二卤代苯酚，然后由所得到的二卤代苯酚制备卤代苯氧基脂肪酸衍生物。所说的二卤代苯酚是通过在日本专利公开号60-193939、62-223140和3-99033以及日本专利公告(通过审查的公开)号3-22377中所描述的方法来制备的。
然而，这些方法包括产生作为副产物的有毒的二喔星的可能性。此外，除使用氯化剂外，还必须使用过氧化氢(在日本专利公开号62-223140中的方法)、含氮碱(在日本专利公告(通过审查的公开)号3-22377中的方法)和水及两相体系(在日本专利公开号3-99033中的方法)。
此外，作为由卤化一卤代苯氧基脂肪酸衍生物来制备卤代苯氧基脂肪酸衍生物的方法，其被报道是使用卤化剂和催化剂如碘和铁来进行所说的卤化反应[J.O.C.,426(1946)]。然而，这种方法存在所使用的催化剂的后处理问题。
本发明人已做出了深入细致的研究工作，以便开发一种在不使用催化剂的情况下以高的收率制备卤代苯氧基脂肪酸衍生物的新方法，做为结果，已完成了本发明。
通过本发明的方法制备的由式(Ⅰ)表示的卤代苯氧基脂肪酸衍生物用做药物、农业化学品和化学产品的中间体，并且它们中的某些由下述式(Ⅰ′)表示的化合物是新化合物(至今在文献中没有记载)。式中，R′代表氰基或-CON(R3′)R4′(其中R3′和R4′可相同或不同，每个代表氢原子，低级烷基，苯基，具有相同或不同的1至5个取代基的苯基，其取代基选自卤原子、硝基、氰基、低级烷基、低级卤代烷基、低级烷氧基、低级卤代烷氧基、低级烷基硫代基和低级卤代烷基硫代基，苄基或具有相同或不同的1至5个取代基的苄基，其取代基选自低级烷基、低级卤代烷基、低级烷氧基、低级卤代烷氧基、低级烷基硫代基和低级卤代烷基硫代基)，R1′和R2′可相同或不同，每个代表氢原子或低级烷基，X′代表氟原子、碘原子、溴原子或低级烷基和Y′代表卤原子，限定条件是，当R1′和R2′代表氢原子，X′代表氟原子和Y′代表氯原子时，R′不能代表氰基。
本发明的卤代苯氧基脂肪酸衍生物可通过例如下述的图解来制备。
Figure C9310450600072
(式中R、R1、R2、X和Y定义如上)。
目的卤代苯氧基脂肪酸衍生物可在惰性溶剂存在下用卤化剂通过卤化由式(Ⅱ)表示的苯氧基脂肪酸来选择性地制备。
本发明中所使用的惰性溶剂可以是任何不明显阻碍上述反应进行的那些溶剂，所说溶剂的实例为卤代烃，如二氯甲烷、氯仿、四氯化碳和全氯乙烯；羧酸，如甲酸、乙酸或丙酸；芳烃，如硝基苯、氯苯、二氯苯和三氯苯；酯，如乙酸乙酯；腈，如乙腈和苄腈；酰胺，如二甲基甲酰胺和二甲基乙酰胺；环丁砜，二甲砜，二甲亚砜，1,3-二甲基-2-咪唑啉酮和水，这些惰性溶剂每一种可以单独使用或以混合的形式使用。
作为卤化剂，可以使用如氯、溴、碘、盐酸-过氧化氢、硫酰氯、五氰化磷、N,N-二氯脲、N-氯琥珀酰亚胺、N-溴琥珀酰亚胺、次卤酸叔丁基酯、三氯异氰脲酸和三氯甲磺酰卤化物。每摩尔由式(Ⅱ)表示的苯氧基脂肪酸所用的卤化剂的量可任意选择的范围为0.1摩尔至过量摩尔的量。
如果需要的话，在本发明的方法中，可使用有机碱、无机碱或有机盐。有机碱的实例为胺，如三乙胺和吡啶；无机碱的实例为碱金属或碱土金属的氢氧化物，如氢氧化钠、氢氧化钾、氢氧化钙和氢氧化钡及碱金属或碱土金属的碳酸盐，如碳酸钠、碳酸钾和碳酸钙，以及有机盐的实例为有机酸的碱金属或碱土金属盐，如乙酸钠、乙酸钾、乙酸钙和苯甲酸钠以及乙酸铵。每摩尔由式(Ⅱ)表示的苯氧基脂肪酸的用量可任意选择的范围为0.1摩尔至过量摩尔的量。
反应温度可任意选择的范围为-20℃至所使用的惰性溶剂的沸点。
反应时间取决于反应温度和反应程度，但可选择的范围为几分钟至48小时。
反应完成后，含有目的产物的反应混合物可用常规方法，如用溶剂萃取来分离。如果需要，可用柱色谱、重结晶、蒸馏或类似的方法进行提纯，由此可制备由式(Ⅰ)或(Ⅰ′)表示的卤代苯氧基脂肪酸衍生物。
由式(Ⅰ)表示的新化合物卤化苯氧基脂肪酸衍生物的具有代表性的实例示于表Ⅰ中。表1
Figure C9310450600092
在“性质”一栏中表示“油状物”的上述表1中的化合物的NMR数据示于表2中。
                             表2
    No.     1H-NHR(CDCl3,PP*
    8 1.63(3H,d),4.97(1H,m),6.99(1H,m)7.08(1H,d.d),7.17(1H,d.d)
    9 2.27(3H,s),4.49(2H,S),5.64(1H,br),6.79(1H,br),6.80(1H,d),7.02(1H,d.d),7.20(1H,d)
通过下述的不受限制的典型实施例来说明本发明。
实施例1．制备2-氯-4-氟苯氧基乙腈(化合物No.25)
1.51g(0.01mol)4-氟苯氧基乙腈和0.82g(0.01mol)乙酸钠溶于含有7ml乙酸和3ml水的混合溶剂中，并于50℃下以12.3ml/分的速率将氯气导入该溶液中达60分钟，同时进行搅拌。
该反应结束后，向反应混合物中加入3ml 10％硫代硫酸钠水溶液并在减压下蒸镏出溶剂。向所得残余物中加入20ml 10％碳酸氢钠水溶液，并用乙酸乙酯(30ml×2)萃取目的产物。
有机层经无水硫酸钠干燥并在减压下浓缩。蒸镏所得浓缩物得到1.54g 2-氯-4氟苯氧基乙腈。
该化合物为已知化合物，其具有与文献中记载相同的熔点和NMR数据。
收率：83.0％。
实施例2制备2,4-二氯苯氧基乙酰胺(化合物No:10)
Figure C9310450600111
在50℃下加热的同时，将1.86g(0.01mol)4-氯苯氧基乙酰胺溶于11ml乙酸中，并在此温度下以12.3ml/分的速率向其中导入氯气达50分钟。
反应结束后，向该反应混合物中加入3ml 10％硫代硫酸钠水溶液并在减压下蒸镏出溶剂。向该残余物中加入20ml 10％碳酸氢钠水溶液并将目的产物用乙酸乙酯(30ml×2)萃取。
有机层经无水硫酸钠干燥并在减压下浓缩。所得晶体用正己烷洗涤得到2.02g目的产物2,4-二氯苯氧基乙酰胺。
收率92.0％
该化合物为已知化合物，其具有与文献中记载相同的熔点和NMR数据。
实施例3，制备2,4-二氯苯氧基乙酸(化合物No:17)
Figure C9310450600112
1.87g(0.01mol)4-氯苯氧基乙酸加入到10ml二甲基甲酰胺中并在搅拌的同时于50℃下以12.3ml/的速率向其中导入氯气达45分钟。
反应结束后，向该反应混合物中加入3ml 10％硫代硫酸钠水溶液并在减压下蒸镏出溶剂。向该残余物中加入20ml 10％碳酸氢钠水溶液并用乙酸乙酯(30ml×2)萃取目的产物。
有机层经无水硫酸钠干燥并在减压下浓缩。所得晶体用正己烷洗涤得到2.07g目的产物2,4-二氯苯氧基乙酸。
收率：93.6％。
该化合物为已知化合物，其具有与文献中记载相同的熔点和NMR数据。
表3示出了按照与实施例1-3相同的方法制备的由式(Ⅰ)表示的卤代苯氧基脂肪酸衍生物的典型实施例。
因为示于表3中的化合物为已知化合物，其通过与文献中记载的相同熔点；NMR和IR数据来鉴别。表3
Figure C9310450600132
由式(Ⅰ)表示的卤代苯氧基脂肪酸衍生物是重要的化合物，特别是作为制备除草剂(公开于日本专利公开号3-163063中)的中间体。
做为最终产物的典型除草剂可通过如下述的用图解表示的方法来制备。
式中R、R1、R2、X和Y定义如上，R3″代表低级烷氧基，R4″代表低级烷基或低级卤代烷基，R5″代表低级烷基或低级卤代烷基，和Hal代表卤原子。

Claims (4)

1．制备由式(Ⅰ)表示的卤代苯氧基脂肪酸衍生物的方法，
Figure C9310450600021
式中R代表氰基，-CON(R3)R4或-COAR5，其中R3和R4可相同或不同，每个代表氢原子，低级烷基，苯基，具有相同或不同的1至5个取代基的苯基，其取代基选自卤原子、硝基、氰基、低级烷基、低级卤代烷基、低级烷氧基、低级卤代烷氧基、低级烷基硫代基和低级卤代烷基硫代基，苄基或具有相同或不同的1至5个取代基的苄基，其取代基选自低级烷基、低级卤代烷基、低级烷氧基、低级卤代烷氧基、低级烷基硫代基和低级卤代烷基硫代基，并且R3和R4可一起代表亚烷基；R5代表氢原子，低级烷基，苯基，具有相同或不同的1至5个取代基的苯基，其取代基选自卤原子、硝基、氰基、低级烷基、低级卤代烷基、低级烷氧基、低级卤代烷氧基、低级烷基硫代基和低级卤代烷基硫代基，苄基或具有相同或不同的1至5个取代基的苄基，其取代基选自低级烷基，低级卤代烷基、低级烷氧基、低级卤代烷氧基、低级烷基硫代基和低级卤代烷基硫代基，和A代表氧原子或硫原子；R1和R2可相同或不同，每个代表氢原子或低级烷基，X代表卤原子或低级烷基和Y代表卤原子，该方法包括，在卤化剂存在下，选择性卤化由式(Ⅱ)表示的苯氧基脂肪酸
Figure C9310450600031
其中R、R1、R2和X定义如上。
2．根据权利要求1的方法，其中的卤化剂为氯化剂。
3．由式(Ⅰ′)表示的卤代苯氧基脂肪酸衍生物：
Figure C9310450600032
其中R′代表氰基或-CON(R3′)R4′，其中R3′和R4′可相同或不同，每个代表氢原子，低级烷基，苯基，具有相同或不同的1至5个取代基的苯基，其取代基选自卤原子、硝基、氰基、低级烷基、低级卤代烷基、低级烷氧基、低级卤代烷氧基、低级烷基硫代基、和低级卤代烷基硫代基，苄基或具有相同或不同的1至5个取代基的苄基，其取代基选自低级烷基、低级卤代烷基、低级烷氧基、低级卤代烷氧基、低级烷基硫代基和低级卤代烷基硫代基；R1′和R2′可相同或不同，每个代表氢原子或低级烷基，X′代表氟原子、碘原子、溴原子或低级烷基、和Y代表卤原子，限定条件是，当R1′和R2′代表氢原子，X′代表氟原子和Y′代表氯原子时，R′不代表氰基。
4．根据权利要求3的卤代苯氧基脂肪酸衍生物，其中式(Ⅰ′)中的R′代表氰基或-CON(R3′)R4′，其中R3′和R4′可相同或不同，每个代表氢原子，低级烷基，苯基或具有相同或不同的1至5个卤原子取代基的苯基，并且R3′和R4′可一起代表亚烷基；R1′代表氢原子或低级烷基，R2′代表氢原子，X′代表氟原子或低级烷基和Y′代表氯原子。
CN93104506A 1992-03-26 1993-03-25 选择性卤化制备卤代苯氧基脂肪酸衍生物的方法和卤代苯氧基脂肪酸衍生物 Expired - Fee Related CN1043228C (zh)

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