CN1238565C - 卤代的4－氨基吡啶甲酸的选择性电化学还原 - Google Patents
卤代的4－氨基吡啶甲酸的选择性电化学还原 Download PDFInfo
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Abstract
本发明公开了一种在3-和6-位卤素取代基的存在下通过电解选择性地还原4-氨基吡啶甲酸的5-位的卤素取代基的方法。
Description
本发明涉及通过电化学还原制备某些4-氨基吡啶甲酸的方法。更具体地说，本发明涉及在3-和6-位卤素取代基存在下选择性地还原卤代的4-氨基吡啶甲酸的5-位的卤素取代基的方法。
最近，已经发现5-位含有氢的某些4-氨基-3-卤代吡啶甲酸的衍生物可用作除草剂。因此，需要能够从相应的5-卤代衍生物制备这些除草剂，其中许多诸如4-氨基-3，5，6-三氯-吡啶甲酸(毒莠定)之类的衍生物是商业上可得的。
虽然卤代吡啶的化学还原是公知的，例如，参见美国专利4,087,431，其中利用肼作为还原剂，但是材料利用的效率低并且成本相对较高。另一方面，电解还原非常有效并具有选择性。美国专利3,694,332公开了4-位的卤代吡啶和卤代氰基吡啶的选择性电解还原。美国专利4,217,185公开了4-和5-位的四氯吡啶甲酸的电解还原。美国专利4,242,183公开了利用活化的银网阴极将对称的四氯吡啶电解还原成2，3，5-三氯吡啶的方法。该专利还要求了活化银阴极的方法。俄国专利SU 1807686 A1公开了多氯吡啶羧酸的电解还原。上述的选择性电解还原都限于仅含有羧酸或氰基取代基的卤代吡啶。因此，需要能选择性地还原含其它取代基的卤代吡啶的电化学方法。
现在，已经发现本发明通过相应的4-氨基-3，5-二卤代吡啶甲酸的电化学还原可制备4-氨基-3-卤代吡啶甲酸。更具体地说，本发明涉及制备结构式I的4-氨基-3-卤代吡啶甲酸的方法，
其中：
X表示Cl或Br；
Y表示H、F、Cl、Br或C1～C4烷基；和
R彼此独立地表示H或C1～C4烷基，
该方法包括将直流或交流电流从阳极到阴极经过结构式II的4-氨基-3，5-二卤代吡啶甲酸的溶液，
其中：
X、Y和R的定义如前，和
其中：
两个X或者是Cl或者是Br，
当X是Cl时，Y不是Br，阴极电势相对于Ag/AgCl参比电极为-0.4～-1.7伏，其中AgCl溶液中的Cl-浓度为3.0M；以及回收产物。出人意料地是，在4-氨基存在下5-位的卤素被高产率地选择性除去。
在此所用的术语“卤素”或“卤代”是指Cl或Br。
下面描述在4-氨基-3，5-二卤代吡啶甲酸的还原中所涉及的反应：
A)中和反应：
B)阴极反应：
C)阳极反应：
D)总反应：
这样进行羧酸的回收：酸化该反应混合物并利用传统的技术回收产物。
通过本领域通常公知的技术进行所需的电解还原。一般地，将原始的4-氨基-3，5-二卤代吡啶甲酸溶于溶剂中而形成电解质，将该电解质加入到电解池中，同时施加足够的电流经过电解质，直到得到所需程度的还原。
本领域的技术人员应该领会到，溴的还原电势比参照氯电势高约0.5伏(更小的负值)。溴总是首先被还原。因此，当X是Cl时，Y不能是Br。
电解池的设计不是关键性的。电解可间歇进行或以连续或半连续方式进行。电解池可以是含有电极的搅拌槽或任何传统设计的流动电解池。在某些情况下，需要使用分离器将电解池分成独立的阳极和阴极隔室。有用的分离器材料的例子是各种阴离子和阳离子交换膜、多孔的Teflon、石棉和玻璃。虽然优选使用相对于参比电极能控制阴极电势的三个电极，但是电解也可仅利用两个电极(阳极和阴极)并控制电池电流、电池电压或两者来进行。为了方便，优选其中将电解质用作阴极电解液和阳极电解液的3-电极的未隔开电池。
阳极可以是任何化学惰性材料，包括例如铂、石墨、碳、诸如银上的氧化银之类的金属氧化物或诸如Hastelloy C之类的合金，优选石墨、碳和Hastelloy C。类似地，阴极可从许多材料制备，包括汞、铅、铁、锡、锌或银，优选银。电极可以是板极、杆状、导线、筛网、网状、羊毛状、片状或弓弧状的形式，优选扩展的筛网。阳极或阴极还可由涂覆到另一种材料上的涂层组成，其中的一个例子是将诸如氧化钌之类的贵金属氧化物涂布到钛上。
最优选的阴极是按照记载于美国专利4,217,185和4,242,183中的方法制备的活化的银阴极。该活化的阴极通过将银微晶层沉积在导电基片上来制备，从而形成复合电极，或通过银电极自身的阳极化来制备。例如，为了说明后者，将未活化的银电极浸入苛性碱液的阴极电解液中并对其进行阳极氧化，因此将电极表面的一些银转化成胶态的氧化银并同时将表面变粗糙。然后将电极的极性倒转，可转化成微晶银粒子的可电解的氧化物粘附到电极表面上。活化步骤包括将电势从初值零伏增加到终值至少+0.3伏，优选+0.7伏。氧化物沉积物的还原需要阴极的负极化。阴极电势通常从氧化步骤中达到的值+0.3～+0.7伏逐渐减小到数值-0.5伏或更小。在该方法中，不需要将任何银加入到阴极电解液或碱液中。
水是用于电解的最优选溶剂，但是，在某些情况下，能够单独或作为共溶剂使用有机溶剂。该溶剂或共溶剂体系应该溶解所有的或多数起始材料和电解质，或者至少能够使还原以适当速率进行。另外，该溶剂或共溶剂体系对于电解条件呈惰性，也就是说，其不能不利地改变或与阴极或阴极电解液材料发生反应到无法忍受的程度。除了水，优选的溶剂/共溶剂是和水可混溶的物质，包括较低分子量的醇、诸如四氢呋喃、二噁烷和聚乙二醇醚之类的醚和诸如二甲基甲酰胺或二甲基乙酰胺之类的低分子量酰胺。
碱金属氢氧化物优选作为支持电解质，但是也可以使用诸如季铵或金属氢氧化物、氯化物、碳酸盐等之类的许多其它物质。NaOH是最优选的支持电解质。
在反应中，需要1当量的碱中和起始材料，并需要另一当量的碱来产生在电解中消耗的氢氧根离子。该反应通常在碱过量条件下，优选在整个反应中碱过量0.05～2wt％的条件下进行。
阴极电解液或原料中卤代的4-氨基吡啶甲酸的浓度为1～20wt％，优选8～12wt％。较低的浓度降低了生产率，但是较高的浓度通常导致更低的产量、更低的产物纯度和更低的电效率。
用于电解的适当温度为5～90℃。优选温度为20～60℃。最优选20～40℃。
本领域的技术人员可领会到，卤素被选择性地还原的表观阴极电势与多种因素有关，例如，该因素包括特定反应物的结构、电池构型和分离电极之间的距离。一般地，阴极电势相对于标准Ag/AgCl(3.0MCl-)电极对于Br为0.4～-1.1伏、对于Cl为-0.8～-1.7伏。对于Br，优选阴极电势为-0.6～-0.9伏。对于Cl，优选阴极电势为-1.0～-1.4伏。以安培/平方厘米表示的电流密度(A/cm2)至少为0.005，优选0.05A/cm2或更大。
虽然优选放出氧分子，但是也可以使用许多其它的阳极反应。该例子包括氯分子和溴分子的放出、通过诸如甲酸盐或草酸盐之类的保护性物质的氧化来产生二氧化碳或通过有机反应物的氧化来形成有价值的副产物。
在目前优选的操作方式中，将卤代的4-氨基吡啶甲酸溶于苛性碱液中而形成碱性水溶液，将该碱性水溶液经过未分开的电解池连续地进行循环，该电解池具有在苛性碱液电解质中于+0.7伏通过阳极化而被活化的扩展银筛网阴极。在将反应混合物保持碱性的同时，于相对于Ag/AgCl(3.0M Cl-)参比电极为-0.6～-1.5伏的阴极电势条件下继续进行电解，直到出现所需程度的还原。通过传统技术回收目的产物。例如，通过酸化将酸从反应混合物中沉淀出来，然后或者进行过滤，或者用与水不溶的有机溶剂进行萃取。
下面的实施例是对本发明的说明。
实施例
实施例1
4-氨基-3，6-二氯吡啶-2-甲酸的制备(溢流电池)
向3升(L)的烧杯中加入2000克(g)热水、115.1g 50wt％NaOH和200g潮湿的4-氨基-3，5，6-三氯吡啶-2-甲酸(79.4％)。将该溶液搅拌30分钟，通过纸滤器进行过滤并转移到5L进料/循环槽中。将该溶液称重为2315g，并含有6.8％4-氨基-3，5，6-三氯吡啶-2-甲酸。将该进料以约9.46 L/min的速率于30℃下经过未分开的电解池进行循环，该电解池具有Hastelloy C阳极(15cm×4cm)和扩展的银筛网阴极(15cm×4cm)。在+0.7伏(v)进行标准的阳极化后，将电池的极性倒转并开始进行电解。将阴极工作电势相对于Ag/AgCl(3.0M Cl-)参比电极控制在-1.1～-1.4v。该参比电极实际上直接位于银阴极的后面并与含水盐桥进行连接。在循环进料的同时，将50％NaOH溶液缓慢地泵入到循环槽中，从而将NaOH浓度维持在过量1.5～2.0％。电流范围为1.0～5.2安培。
约15小时(h)以及约213,100库仑的电量经过体系后，将电解终止，并通过纸滤器将电池流出物进行过滤。将该溶液用浓HCl进行中和并浓缩至约750g粗浓缩液。将该粗浓缩液在搅拌中加热至85℃，用浓HCl在30分钟内将pH调节到小于1。将生成的浆液冷却到室温并进行过滤。将滤饼用200毫升(mL)的水洗涤3次并于80℃进行真空干燥。经分析，干燥的产物(118.1g)含有90.6％目的产物；气相色谱(GC)显示含有约4％的4-氨基-3，5，6-三氯吡啶-2-甲酸杂质。4-氨基-3，6-二氯吡啶-2-甲酸的纯化后的样品熔点(mp)为185-187℃(摄氏度)；1H NMR(DMSO-d6)：δ13.9(br，1H)，7.0(br m，2H)，6.8(s，1H)；13C NMR{1H}(DMSO-d6)：δ165.4(1C)，153.4(1C)，149.5(1C)，147.7(1C)，111.0(1C)，108.1(1C)。
实施例2
4-氨基-3，6-二氯吡啶-2-甲酸的制备(间歇式电池)
电解池是180mL烧杯(2英寸(5.1cm)直径×4.5英寸(11.4cm)高)。银筛网阴极由1英寸(2.5cm)×4英寸(10.2cm)的长条组成，并将其置于烧杯内壁离底部约0.5英寸(1.3cm)处，有0.5英寸(1.3cm)宽的长条从烧杯的顶部延伸出来并将电源附着在其上。阳极是0.75英寸(1.9cm)直径×6英寸(15.2cm)长的石墨棒，该石墨棒用烧杯中间的橡胶塞子支撑并延伸至离底部约0.5英寸(1.3cm)处。将阴极的工作电势相对于Ag/AgCl(3.0M Cl-)参比电极进行控制，该参比电极位于银筛网和烧杯壁之间。
将银筛网阴极于+0.7伏(v)在2％氢氧化钠和1％氯化钠的水溶液中通过阳极氧化、然后进行反向极化来对其进行活化。活化后，将该溶液用81mL水、5.1g(0.0213摩尔)4-氨基-3，5，6-三氯吡啶甲酸和2.8g(0.0426摩尔)85％KOH组成的溶液代替。用缓慢的氮气流喷射后，在室温下于工作电势为-1.3～-1.35伏的条件下电解2小时。起始电流为0.83安培，2小时后逐渐地减小到0.25安培。5000库仑的总电量经过该溶液(理论上将吡啶环上的一个氯进行还原的电量是2050库仑)。对粗产物溶液进行梯度洗脱HPLC分析表明，起始材料消失并出现单峰，该单峰随后鉴定为4-氨基-3，6-二氯吡啶甲酸。
实施例3
4-氨基-3，6-二溴吡啶-2-甲酸的制备(间歇式电池)
使用与实施例2相同的间歇式电解池。向电解池中加入75mL 1％氯化钠和2％氢氧化钠的水溶液。将银阴极进行活化，然后向电池内的溶液中加入0.635g 4-氨基-3，5，6-三溴吡啶甲酸甲酯。将该溶液加热至约75℃并保持30分钟，从而将酯水解成羧酸酯阴离子后，将该溶液冷却到室温。在阴极工作电势为-0.7伏的条件下电解45分钟。起始电流为0.44安培，在反应终点电流下降到0.12安培。通过了400库仑的总电量。
将电解溶液进行回收，将溶液的pH调节到中性并将该溶液进行蒸发干燥。将回收后的固体溶于乙腈和水的混合物中，并通过准备的HPLC回收产物。得到单一异构体的110mg样品，经HPLC和1H NMR分析表明该样品的纯度＞98％，经鉴定该样品为4-氨基-3，6-二溴吡啶甲酸。
Claims (9)
1.一种制备结构式I的4-氨基-3-卤代吡啶甲酸的方法，
其中
X表示Cl或Br；
Y表示H、F、Cl、Br或C1～C4烷基；和
R彼此独立地表示H或C1～C4烷基，
该方法包括将直流或交流电流从阳极到阴极经过结构式II的4-氨基-3，5-二卤代吡啶甲酸的溶液，
其中
X、Y和R的定义如前，和
其中
两个X或者是Cl或者是Br，
当X是Cl时，Y不是Br，阴极电势相对于Ag/AgCl参比电极为
-0.4～-1.7伏，其中AgCl溶液中Cl-浓度为3.0M，以及回收产物。
2.如权利要求1所述的方法，其中结构式II的化合物是
其中X和Y的定义如前。
3.如权利要求1所述的方法，其中4-氨基-3，5-二卤代吡啶甲酸的溶液是碱性水溶液。
4.如权利要求1所述的方法，其中X是Cl，阴极电势是-0.8～-1.7伏。
5.如权利要求4所述的方法，其中Y是Cl。
6.如权利要求1所述的方法，其中X是Br，阴极电势为-0.4～-1.1伏。
7.如权利要求6所述的方法，其中Y是Br。
8.如权利要求1所述的方法，其中阴极是银。
9.如权利要求8所述的方法，其中银阴极通过在苛性碱液中于电势为+0.3～+0.7伏的条件下阳极氧化，然后将电极的极性倒转来进行活化。
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| UA81177C2 (uk) * | 2003-08-04 | 2007-12-10 | Дау Агросайєнсіз Ллс | 6-(1,1-дифторалкіл)-4-амінопіколінати та їх використання як гербіцидів |
| EP1526192A1 (de) * | 2003-10-24 | 2005-04-27 | Siemens Aktiengesellschaft | Elektrolytisches Verfahren zum Abscheiden einer gradierten Schicht auf ein Substrat und Bauteil |
| TWI406849B (zh) * | 2006-10-04 | 2013-09-01 | Dow Agrosciences Llc | 鹵化４-胺基吡啶甲酸之經改良的電化學還原反應 |
| US7666293B2 (en) * | 2007-10-04 | 2010-02-23 | Dow Agrosciences Llc | Electrochemical reduction of halogenated 4-aminopicolinic acids |
| ITMI20081282A1 (it) * | 2008-07-15 | 2010-01-16 | Industrie De Nora Spa | Processo di trattamento di reflui industriali |
| CN101603179B (zh) * | 2009-06-29 | 2013-11-06 | 浙江工业大学 | 3,5,6-三氯吡啶甲酸的电解合成方法 |
| WO2011053582A1 (en) | 2009-10-27 | 2011-05-05 | Dow Agrosciences Llc | Improved silver cathode activation |
| TWI529163B (zh) * | 2011-01-25 | 2016-04-11 | 陶氏農業科學公司 | 用於製備４－胺基－５－氟－３－鹵素－６－（經取代之）吡啶甲酸酯的方法 |
| CN102358944A (zh) * | 2011-08-23 | 2012-02-22 | 哈尔滨理工大学 | 一种氨基吡啶氯化物的制备方法 |
| JP6167114B2 (ja) * | 2012-01-31 | 2017-07-19 | カウンシル オブ サイエンティフィック アンド インダストリアル リサーチ | ナノ構造の酸化銀膜使用の水性ボルタンメトリー農薬センサおよびそのセンサの製造方法 |
| CN104988531B (zh) * | 2015-07-07 | 2017-11-07 | 浙江工业大学 | 一种氯代吡啶甲酸电催化选择性脱氯制备吡啶甲酸的方法 |
| CN105803481B (zh) * | 2016-03-22 | 2018-03-27 | 浙江埃森化学有限公司 | 一种催化电解制备4‑氨基‑3,6‑二氯吡啶‑2‑甲酸的方法 |
| CN105887129B (zh) * | 2016-05-16 | 2017-12-29 | 浙江工业大学 | 一种三氯甲基吡啶衍生物电化学选择性脱氯制备甲基吡啶衍生物的方法 |
| CN105887127B (zh) * | 2016-05-16 | 2017-12-29 | 浙江工业大学 | 一种电化学选择性脱氯制备氯甲基吡啶衍生物的方法 |
| CN107778226B (zh) * | 2016-08-26 | 2019-07-02 | 利尔化学股份有限公司 | 一种4-氨基-3，6-二氯吡啶-2-甲酸的纯化方法 |
| CN108611656B (zh) * | 2016-12-12 | 2019-07-30 | 利尔化学股份有限公司 | 一种4-氨基-3,6-二氯吡啶-2-甲酸的合成方法 |
| CN109763138A (zh) * | 2017-11-09 | 2019-05-17 | 山东润博生物科技有限公司 | 一种3,6-二氯水杨酸的制备方法 |
| CN114075675B (zh) * | 2021-11-18 | 2023-09-29 | 永农生物科学有限公司 | 电解脱氯合成4-氨基-3,6-二氯吡啶甲酸的方法及产品和应用 |
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| US4217185A (en) * | 1979-07-02 | 1980-08-12 | The Dow Chemical Company | Electrolytic production of certain trichloropicolinic acids and/or 3,6-dichloropicolinic acid |
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| EP1248867A1 (en) | 2002-10-16 |
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| JP2003519726A (ja) | 2003-06-24 |
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| ATE247726T1 (de) | 2003-09-15 |
| WO2001051684A1 (en) | 2001-07-19 |
| TR200301395T4 (tr) | 2004-04-21 |
| CZ296504B6 (cs) | 2006-03-15 |
| MXPA02006890A (es) | 2003-01-28 |
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| PL355993A1 (en) | 2004-05-31 |
| DE60100620D1 (de) | 2003-09-25 |
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