CN1100758C - [(5,6－二羧基－3－吡啶基)甲基]卤化铵的制备方法 - Google Patents
[(5,6－二羧基－3－吡啶基)甲基]卤化铵的制备方法 Download PDFInfo
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Abstract
本发明提供了制备结构式I的[(5，6-二羧基-3-吡啶基)甲基]卤化铵的方法[(5，6-二羧基-3-吡啶基)甲基]卤化铵是制备除草剂5-(烷氧基甲基)-2-(2-咪唑啉-2-基)-烟酸、酯、盐化合物中有用的中间体。
Description
本发明涉及[(5，6-二羧基-3-吡啶基)甲基]卤化铵的制备方法。
[(5，6-二羧基-3-吡啶)甲基]卤化铵是制备除草剂5-(烷氧基甲基)-2-(2-咪唑啉-2-基)烟酸、酯和盐化合物中有用的中间体。美国专利5,378,834揭示了将5-甲基-2，3-吡啶二羧酸衍生物转化为[(5，6-二羧基-3-吡啶)甲基]卤化铵的方法。虽然该专利的方法是有用的，人们尚在努力发现制备[(5，6-二羧基-3-吡啶)甲基]卤化铵的新方法。
因此，本发明的一个目的是提供制备[(5，6-二羧基-3-吡啶)甲基]卤化铵的高效的方法。
本发明提供了制备结构式I的[(5，6-二羧基-3-吡啶)甲基]卤化铵，它的N-氧化物，或它的酸加成盐的高效方法：
其中R、R1和R2各自是C1-C4烷基，当结合在一起时，R和R1可形成任意被O、S或NR3间隔的5-元或6-元环；
R3是C1-C4烷基，
X是Cl、Br或I；
Z是氢或卤素；和
Z1是氢、卤素、氰基或硝基，
该方法包括在含水碱存在下用过氧化氢使结构式II的取代的(3-喹啉基甲基)卤化铵氧化
其中R、R1、R2、X、Z和Z1的定义与上式I的相同；
R4、R5、R6和R7各自是氢、羟基、硝基、OC(O)R8、卤素、NR9R10、C1-C4烷氧基、SO3H、SO2Cl或SH，条件是R4、R5、R6和R7中的一个不是氢或卤素；
R8是C1-C4烷基、C1-C4烷氧基、苯基或NR11R12；
R9、R10、R11和R12各自是氢、C1-C4烷基或苯基。
在本发明一个较好的技术方案中，式II代表的取代的(3-喹啉基甲基)卤化铵用至少约8摩尔当量的过氧化氢在至少约1摩尔当量，较好的是约4-10摩尔当量含水碱存在下，较好地在约50-100℃温度范围下，更好地在约75-95℃温度范围下进行氧化。
现已发现，有利的是通过本发明的高效方法可高得率、高纯度地得到[(5，6-二羧基-3-吡啶)甲基]卤化铵。
通过用无机酸酸化反应混合物，并通过标准方法收集所得的式I产物可分离得到产物[(5，6-二羧基-3-吡啶)甲基]卤化铵。另一种方法是，将反应混合物整体用于制备最终除草剂的方法而不分离式I化合物。
上述Z、Z1、R4、R5、R6和R7的卤素例子是氟、氯、溴和碘，氯较佳。
适用于本发明方法的含水碱包括碱金属氢氧化物，如氢氧化钠和氢氧化钾，碱土金属氢氧化物，如氢氧化钙，碱金属碳酸盐，如碳酸钠和碳酸钾，碱土金属碳酸盐，如碳酸钙，和它们的混合物。较好的含水碱包括含水氢氧化钠和含水氢氧化钾。
有利的是，式II的取代的(3-喹啉基甲基)卤化铵在碱水溶液中的溶解度很高。一般来说，较好的碱浓度约为35-65wt％，最好的约为40-60wt％。过去，某些喹啉在浓度直至约35wt％含水碱存在下用过氧化氢氧化(参见U.S.4,816,588)。但是，需要适用更高浓度的碱，因为它会减少废物水溶液的生成。本发明方法另一个优点是不需要水相溶混的共溶剂，因为取代的(3-喹啉基甲基)卤化铵在碱水溶液中的溶解度很高。
为了完成式II取代的(3-喹啉基甲基)卤化铵的完全氧化，需要最少为8摩尔当量过氧化氢。较好的是使用约8-60摩尔当量的30-50％过氧化氢水溶液，最好是使用约8-40摩尔当量30-50％过氧化氢水溶液以氧化式II化合物。
在本发明较好的方法中，R、R1和R2各自是C1-C4烷基；
X是Cl或Br；
Z和Z1是氢；
R4、R5、R6和R7中的至少一个是羟基、硝基或OC(O)R8；
R8是C1-C4烷基、C1-C4烷氧基或苯基。
在本发明最好的方法中，R、R1和R2是甲基；
X是Br；
R5、R6、R7、Z和Z1是氢；
R4是羟基、硝基或OC(O)R8；
R8是C1-C4烷基或C1-C4烷氧基。
可这样制备式II的取代的(3-喹啉基甲基)卤化铵：在溶剂和任选地在催化量自由基引发剂存在下，用卤化剂卤化式III的取代的3-甲基喹啉，形成式IV的取代的3-卤代甲基喹啉，使式IV化合物与至少约1摩尔当量式V的胺在溶剂存在下反应。反应流程如下列流程I所示。流程I
本发明也提供了制备具有下式的除草剂(5-烷氧基甲基)-2-(2-咪唑啉-2-基)-烟酸、酯和盐化合物的方法
其中Z和Z1的定义同上；
A是O或S；
R12是任意被苯基取代的C1-C4烷基，该苯基又任意被1-3个C1-C4烷基或卤原子所取代；或是
任意被1-3个C1-C4烷基或卤原子所取代的苯基；
R13是C1-C4烷基；
R14是C1-C4烷基、C3-C6环烷基，或R13和R14与相连的原子一起代表任意被甲基取代的C3-C6环烷基；
R15是氢、二低级烷基亚氨基，
任意被下列之一的基团取代的C1-C12烷基：C1-C3烷氧基、卤素、羟基、C3-C6环烷基、苄氧基、呋喃基、苯基、卤代苯基、低级烷基苯基、低级烷氧基苯基、硝基苯基、羧基、低级烷氧基羰基、氰基或三低级烷基铵；
任意被下列之一的基团取代的C3-C12链烯基：C1-C3烷氧基、苯基、卤素或低级烷氧基羰基，或是被两个C1-C3烷氧基或两个卤素取代的C3-C12链烯基；
任意被一个或两个C1-C3烷基取代的C3-C6环烷基；
或是阳离子，较好地是选自碱金属、碱土金属、锰、铜、铁、锌、钴、铅、银、镍、铵和有机铵的阳离子；和
当R13和R14代表不同的取代基时，还有其光学异构体；
该方法包括：
(a)用上述方法制备下式I化合物：
其中Z、Z1、R、R1、R2和X的定义同上；和
(b)将所述的式I化合物转化为式VI化合物。
上面涉及烷基和烷氧基所用的术语“低级”表示含1-6个，较好地含1-4个碳原子的烷基或烷氧基。
可用各种方法将式I化合物转化为式VI化合物。通过结合能将一种羧酸衍生物转化为另一种的反应，人们可以设计出反应途径。
用来制备咪唑啉酮除草剂的方法如“咪唑啉酮除草剂”一书所述，D.L.Shaner和S.L.O’Connor主编，CRC出版社(美国弗罗里达)于1991出版，具体是第2章名为“咪唑啉酮除草剂的合成”8-14页一文，以及其中引述的参考文献。下列专利文献也揭示了可用来将羧酸衍生物转化为咪唑啉酮最终产物的方法：
美国专利5,378,843；5,371,229；5,520,694；5,110,930；5,122,608；5,206,368；4,925,944；4,921,961；4,959,476；5,103,009；4,816,588；4,757,146；4,798,619；4,766,218；5,001,254；5,021,078；4,723,011；4,709,036；4,658,030；4,608,079；4,719,303；4,562,257；4,518,780；4,474,962；4,623,726；4,750,978；4,638,068；4,439,607；4,459,408；4,459,409；4,460,776；4,125,727和4,758,667，以及欧洲专利申请号EP-A-0-041-623；EP-A-0-331,899和EP-A-0-388,619。
为了易于进一步理解本发明，下列实施例仅供阐述更特定的细节用。本发明的范围不为这些实施例所限制，而由权利要求书来定义。
实施例1
[(5，6-二羧基-3-吡啶基)甲基]三甲基溴化铵的制备
在85-90℃下于15分钟内将过氧化氢溶液(20克，30wt％，12当量)加入搅拌着的[(8-乙酰氧基-3-喹啉基)甲基]三甲基溴化铵(5.0g，14.7毫摩尔)溶液和氢氧化钠溶液(9.4g，50wt％，8当量)。所得的反应混合物在85-90℃下搅拌90分钟，在85℃下再用过氧化氢溶液(26克，30wt％，15.6当量)处理30分钟，在85-90℃下搅拌一小时。LC分析最终的反应混合物表示标题产物的得率为80％。
实施例2-4
用与实施例1基本相同的过程，但使用各种[(8-取代-3-喹啉基)-甲基]三甲基溴化胺得到了如表1所示的[(5，6-二羧基-3-吡啶基)甲基]三甲基溴化铵。
表I
[(5，6-二羧基-3-吡啶基)甲基]三甲基溴化铵的制备
| 实施例 | R4 | 50wt％NaOH溶液的当量 | 30wt％H2O2溶液的当量 | 在85-90℃下搅拌的小时 | I的得率％1 |
| 2 | OH | 8 | 38 | 1.83 | 86 |
| 3 | OCO2CH3 | 9.8 | 58 | 1.75 | 83 |
| 4 | NO2 | 8 | 32 | 2.58 | 45 |
1LC分析反应混合物
实施例58-乙酰氧基-3-甲基喹啉的制备
在0-10℃下用乙酸酐(208克，2.04摩尔)处理8-羟基-3-甲基喹啉(200克，1.02摩尔)和氢氧化钠(102克，2.55摩尔)在水(1000毫升)中的混合物达1小时，在室温下搅拌1小时。再加入乙酸酐(50克，0.49摩尔)，所得的混合物搅拌一小时，用饱和碳酸氢钠溶液(100毫升)处理，过滤得到固体。固体用水洗涤，60℃真空烘箱内干燥，用乙酸乙酯/庚烷溶液重结晶得到白色针状的标题产物(168.5g，82％得率)。
实施例68-苯甲酰氧基-3-甲基喹啉的制备
在0-10℃下，于1小时内用苯甲酰氯(10.8g，0.077摩尔)处理8-羟基-3-甲基喹啉(10克，0.051摩尔)和三乙胺(15.5g，0.15摩尔)在二氯甲烷中的混合物，在室温下搅拌三小时，用水稀释。分离各相，有机相用水洗涤，用无水硫酸镁干燥，真空浓缩得到固体。固体用庚烷/甲苯溶液重结晶得到淡黄色晶体的标题产物(8.8g，得率65％)。
实施例7[(8-乙酰氧基-3-喹啉基)甲基]三甲基溴化铵的制备
8-乙酰氧基-3-甲基喹啉(168.5g，0.84摩尔)、N-溴代琥珀酰亚胺(177.9g，1.00摩尔)和2，2’-偶氮二异丁腈(6.7g，0.04摩尔)在氯苯(1，675毫升)中的溶液用氮气冲洗，在氮气下加热到80-90℃达2小时，冷却到室温并过滤。在0-5℃下，滤液在丙酮(700毫升)中的混合物用三甲胺(75.4g，1.28摩尔)处理，在5-10℃搅拌30分钟，在室温下搅拌1小时，过滤得到固体。固体用丙酮洗涤，在60℃的真空烘箱内干燥，得到白色固体的标题产物(180克，总得率63％)。
使用基本相同的内容，但用各种8-取代-3-甲基喹啉得到下列产物
R4OC(O)C6H5OC(O)OCH3
NO2
实施例8[(8-羟基-3-喹啉基)甲基]三甲基溴化铵
将[(8-乙酰氧基-3-喹啉基)甲基]三甲基溴化铵(5.0g，14.7毫摩尔)在甲醇中的溶液回流13.5小时，真空浓缩得到残留物。将残留物在60℃的真空烘箱内干燥得到米色固体的标题产物(4.4g，100％得率)。
Claims (10)
1.一种制备结构式I的[(5，6-二羧基-3-吡啶基)甲基]卤化铵，它的N-氧化物，或它的酸加成盐的方法
其中R、R1和R2各自是C1-C4烷基，当结合在一起时，R和R1可形成任意被O、S或NR3间隔的5-元或6-元环；
R3是C1-C4烷基，
X是Cl、Br或I；
Z是氢或卤素；和
Z1是氢、卤素、氰基或硝基，
该方法包括在含水碱存在下用过氧化氢使结构式II的取代的(3-喹啉基甲基)卤化铵氧化
其中R、R1、R2、X、Z和Z1的定义与上式I的相同；
R4、R5、R6和R7各自是氢、羟基、硝基、OC(O)R8、卤素、NR9R10、C1-C4烷氧基、SO3H、SO2Cl或SH，条件是R4、R5、R6和R7中的一个不是氢或卤素；
R8是C1-C4烷基、C1-C4烷氧基、苯基或NR11R12；
R9、R10、R11和R12各自是氢、C1-C4烷基或苯基。
2.根据权利要求1所述的方法，其中R、R1和R2各自是C1-C4烷基；
X是Cl或Br；
Z和Z1是氢；
R4、R5、R6和R7中的至少一个是羟基、硝基或OC(O)R8；
R8是C1-C4烷基、C1-C4烷氧基或苯基。
3.根据权利要求1所述的方法，其中R、R1和R2是甲基；
X是Br；
R5、R6、R7、Z和Z1是氢；
R4是羟基、硝基或OC(O)R8；
R8是C1-C4烷基或C1-C4烷氧基。
4.根据权利要求1所述的方法，其中过氧化氢的存在量相对于式II的取代的(3-喹啉基甲基)卤化铵为8-60摩尔当量。
5.根据权利要求1所述的方法，其中含水碱的存在量相对于式II的取代的(3-喹啉基甲基)卤化铵至少为1摩尔当量。
6.根据权利要求5所述的方法，其中含水碱的存在量为4-10摩尔当量。
7.根据权利要求1所述的方法，其中含水碱是含水氢氧化钠或含水氢氧化钾。
8.根据权利要求1所述的方法，其中式II的取代的(3-喹啉基甲基)卤化铵用过氧化氢在碱水溶液存在下在50-100℃温度范围里氧化。
9.根据权利要求8所述的方法，其中温度为75-95℃。
10.一种制备具有下式VI的除草剂咪唑啉酮化合物，或其光学异构体的方法：
其中Z和Z1的定义与权利要求1的相同；
A是O或S；
R12是任意被苯基取代的C1-C4烷基，该苯基又任意被1-3个C1-C4烷基或卤原子所取代；或是
任意被1-3个C1-C4烷基或卤原子所取代的苯基；
R13是C1-C4烷基；
R14是C1-C4烷基、C3-C6环烷基，或R13和R14与相连的原子一起代表任意被甲基取代的C3-C6环烷基；
R15是氢、二低级烷基亚氨基，
任意被下列之一的基团取代的C1-C12烷基：C1-C3烷氧基、卤素、羟基、C3-C6环烷基、苄氧基、呋喃基、苯基、卤代苯基、低级烷基苯基、低级烷氧基苯基、硝基苯基、羧基、低级烷氧基羰基、氰基或三低级烷基铵；
任意被下列之一的基团取代的C3-C12链烯基：C1-C3烷氧基、苯基、卤素或低级烷氧基羰基，或是被两个C1-C3烷氧基或两个卤素取代的C3-C12链烯基；
任意被一个或两个C1-C3烷基取代的C3-C6环烷基；
或是阳离子；
该方法包括：
(a)用权利要求1所述的方法制备下式I化合物：
其中Z、Z1、R、R1、R2和X的定义与权利要求1中的相同；和(b)将所述的式I化合物转化为式VI化合物。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66120696A | 1996-06-10 | 1996-06-10 | |
| US08/661206 | 1996-06-10 | ||
| US08/661,206 | 1996-06-10 |
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|---|---|---|---|---|
| US4816588A (en) * | 1986-09-12 | 1989-03-28 | American Cyanamid Company | Method for the preparation of pyridine-2,3-dicarboxylic acids |
| US5378843A (en) * | 1991-12-20 | 1995-01-03 | American Cyanamid Company | 5,6-disubstituted-3-pyridylmethyl ammonium halide compounds useful for the preparation of 5-(substituted methyl)-2,3-pyridinedicarboxylic acids |
| EP0661268A1 (en) * | 1993-12-28 | 1995-07-05 | American Cyanamid Company | Improved method for the preparation of pyridine-2,3-dicarboxylic acids |
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| GB331899A (en) * | 1929-03-08 | 1930-07-08 | Heinrich Schluepmann | Improvements in two-stroke cycle internal combustion engines |
| GB388619A (en) * | 1932-05-26 | 1933-03-02 | Sunsaloon Bodies Ltd | Improvements in beading and cover strips particularly for use on vehicles |
| US4723011A (en) * | 1985-10-28 | 1988-02-02 | American Cyanamid Company | Preparation of substituted and disubstituted-pyridine-2,3-dicarboxylate esters |
| ES2028834T3 (es) * | 1986-09-12 | 1992-07-16 | American Cyanamid Company | Metodo para la preparacion de accidos piridin-2,3-dicarboxilico. |
| IL89142A (en) * | 1988-03-10 | 1993-04-04 | American Cyanamid Co | Method for the sequential oxidation of substituted 8-hydroxyquinolines to produce substituted pyridine-2,3- dicarboxylic acids |
| US5369022A (en) * | 1988-12-30 | 1994-11-29 | American Cyanamid Company | Method to improve the protection of crops from herbicidal injury |
| EP0388619B1 (en) * | 1989-03-22 | 1994-08-10 | American Cyanamid Company | Method for the sequential oxidation of substituted quinolines to produce substituted-pyridine-2,3-dicarboxylic acids |
| US5625068A (en) * | 1995-06-05 | 1997-04-29 | American Cyanamid Company | Substituted quinoline herbicide intermediates and process |
| US5633380A (en) * | 1995-06-05 | 1997-05-27 | American Cyanamid Company | Substituted quinoline herbicide intermediates and process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4816588A (en) * | 1986-09-12 | 1989-03-28 | American Cyanamid Company | Method for the preparation of pyridine-2,3-dicarboxylic acids |
| US5378843A (en) * | 1991-12-20 | 1995-01-03 | American Cyanamid Company | 5,6-disubstituted-3-pyridylmethyl ammonium halide compounds useful for the preparation of 5-(substituted methyl)-2,3-pyridinedicarboxylic acids |
| EP0661268A1 (en) * | 1993-12-28 | 1995-07-05 | American Cyanamid Company | Improved method for the preparation of pyridine-2,3-dicarboxylic acids |
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