CN1238331A - 2位被取代的吡啶的制备 - Google Patents

2位被取代的吡啶的制备 Download PDF

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CN1238331A
CN1238331A CN99105986.7A CN99105986A CN1238331A CN 1238331 A CN1238331 A CN 1238331A CN 99105986 A CN99105986 A CN 99105986A CN 1238331 A CN1238331 A CN 1238331A
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CN1114593C (zh
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马萨·琼·凯利
达米安·杰勒德·韦弗
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Corteva Agriscience LLC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals

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Abstract

本发明涉及用仲丁基锂和任意取代的2－溴代吡啶或2－碘代吡啶通过金属卤素交换而制备2位被取代的吡啶的方法。使所得的锂代吡啶中间体与亲电子试剂反应，以生成所需的2位被取代的吡啶。在上述方法中用仲丁基锂代替正丁基锂，结果导致所需2位被取代的吡啶的产率和纯度均得到提高。

Description

2位被取代的吡啶的制备
本发明涉及用仲丁基锂和被任意取代的2-溴代吡啶或2-碘代吡啶通过金属卤素交换反应而制备2位被取代的吡啶的方法。将所得的锂代吡啶中间体与亲电子试剂反应，以得到所需的2位被取代的吡啶。
2-溴代或2-碘代吡啶和正丁基锂的反应是本领域所熟知的。然而，用该方法只能得到低产率的所需2位被取代的吡啶产物，而且还有反应产物纯度较低的问题。我们意外地发现用仲丁基锂代替上述方法中的正丁基锂，可使该方法制出的所需2位被取代吡啶的产率和纯度提高。
EP0683156A1公开了从2-溴-5-氯代吡啶制备2-乙酰基-5-氯代吡啶的方法，该方法采用正丁基锂做锂化剂，然后再与N,N-二甲基乙酰胺反应以得到产物。然而，该文献没有教导或提示可用仲丁基锂做为锂化试剂及其相应的益处。
本发明提供了式(Ⅰ)所示2位被取代吡啶
Figure A9910598600051
的制备方法，该方法包括如下步骤：(ⅰ)使式(Ⅱ)所示2位被取代吡啶与仲丁基锂反应，生成式(Ⅲ)所示2-锂代吡啶中间体，
Figure A9910598600061
(ⅱ)使式(Ⅲ)所示2-锂代吡啶中间体与亲电子试剂反应，生成式(Ⅰ)所示的2位被取代吡啶，其中：
X是溴或碘，
各式中的Y是在所采用的反应条件下不与所述锂化合物发生反应的基团，
Z是亲电子试剂的残基。
在优选的实施方案中，各式中的Y独立地选自氢原子、氟、氯、烷基、氟代烷基、三氯甲基、烷氧基、氟代烷氧基、烷硫基、氟代烷硫基、N,N-二烷基碳酰胺、苯基和被独立地选自由氟、氯、烷基、氟代烷基、烷氧基、氟代烷氧基、烷硫基、氟代烷硫基和N,N-二烷基碳酰胺所组成的组中的一个或多个基团取代的苯基。
在较为优选的实施方案中，各式中的Y独立地选自如下基团：氢原子、氟、氯、(C1-C4)烷基、氟代(C1-C4)烷基、(C1-C4)烷氧基、氟代(C1-C4)烷氧基、(C1-C4)烷硫基、氟代(C1-C4)烷硫基、N,N-二(C1-C2)烷基碳酰胺、苯基和被一个或多个取代基取代的苯基，所述取代苯基的取代基独立地选自氟、氯、(C1-C2)烷基、氟代(C1-C2)烷基、(C1-C2)烷氧基、氟代(C1-C2)烷氧基、(C1-C2)烷硫基和氟代(C1-C2)烷硫基。
在更为优选的实施方案中，X是溴，各式中的Y独立地选自氢原子、氟、氯、甲基、乙基、甲氧基、乙氧基、三氟甲基和三氟甲氧基。
在最为优选的实施方案中，各式中的Y独立地选自氢原子、氟、氯、三氟甲基和三氟甲氧基。
合适的亲电子试剂是那些与阴离子中间体如式(Ⅲ)所示化合物起反应形成共价键但并不含有能被阴离子中间体如式(Ⅲ)化合物脱质子化的酸性质子的化合物。在优选的实施方案中，所述亲电子试剂选自烷基碘、溴代烷基烷基醚、碘代烷基烷基醚、醛、酮、N,N-二烷基酰胺、烷基磺酸酯、硼酸酯、烷基二硫化物、芳基二硫化物、腈、氯甲酸烷基酯、二氧化碳、三烷基硅氯、氯化三烃基锡、二氧化硫、磺酰氯和带有正电性卤素原子的物质。合适的烷基碘包括，例如，碘代甲烷、碘代乙烷和碘代丙烷。合适的溴代烷基烷基醚包括，例如，溴代甲基甲基醚。合适的碘代烷基烷基醚包括，例如，碘代乙基乙基醚。合适的醛包括，例如，甲醛和苯甲醛。合适的酮包括，例如，二苯甲酮。合适的N,N-二烷基酰胺包括，例如，N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和N-甲酰基哌啶。合适的烷基磺酸酯包括，例如，磺酸二甲酯。合适的硼酸酯包括，例如，硼酸三甲酯和硼酸三异丙酯。合适的烷基二硫化物包括，例如，二甲二硫和二乙化二硫。合适的芳基二硫化物包括，例如，二硫二苯。合适的腈包括，例如，乙腈和丙腈。合适的氯甲酸烷基酯包括，例如，氯甲酸甲酯和氯甲酸乙酯。合适的三烷基硅氯包括，例如，三甲基硅氯。合适的氯化三烃基锡包括，例如，氯化三甲锡。合适的带有正电性卤素原子的物质包括，例如，N-氟代苯磺酰胺、N-氟-O-苯二磺酰胺、N-氟代吡啶鎓盐、N-氯代琥珀酰亚胺和2,2,2-三氟乙基碘。
在优选的实施方案中，亲电子试剂的残基Z为烷基(优选(C1-C6)烷基)、烷氧基烷基(优选(C1-C3)烷氧基(C1-C2)烷基)、烷硫基(优选(C1-C3)烷硫基、苯硫基)、甲酰基、乙酰基、苯甲酰基、羧基或羧化物、氯代磺酸基、磺基或磺酸酯(盐)、烷氧基羰基(优选(C1-C2)烷氧基羰基)、三烷基甲硅烷基(优选(C1-C4)烷基甲硅烷基)、三烃基锡(优选三(C1-C4)烷基锡)或卤素。
“烷基”是指低级烷基链，包括(例如)甲基、乙基、正丙基、正丁基、异丁基、正戊基和正己基。“烷氧基”是指直链或支链烷氧基，包括(例如)甲氧基、乙氧基、异丙氧基和正丙氧基。“烷硫基”是指与硫原子相连的直链或支链烷基，包括(例如)甲硫基、乙硫基、异丙硫基和正丙硫基。“氟代烷基”是指被一个或多个氟原子取代的直链或支链烷基，包括(例如)三氟甲基、全氟乙基和2,2,2-三氟乙基。“氟代烷氧基”是指被一个或多个氟原子取代的直链或支链烷氧基，包括(例如)三氟甲氧基和全氟乙氧基。“氟代烷硫基”是指被一个或多个氟原子取代并与硫原子相连的直链或支链烷基，包括(例如)三氟甲硫基和全氟乙硫基。“N,N-二烷基碳酰胺”是指碳酰胺基中的氮原子被两个烷基取代或与两个烷基一起形成含氮原子的杂环结构，包括(例如)二乙基碳酰胺、二异丙基碳酰胺和N-甲酰基哌啶。
使式(Ⅱ)所示化合物与仲丁基锂化合物反应，生成式(Ⅲ)所示的锂代吡啶中间体，使该中间体与亲电子试剂反应生成式(Ⅰ)所示的2位被取代的吡啶，在上述这些步骤中可采用任何无水的质子惰性溶剂。合适的质子惰性溶剂包括(例如)醚如乙醚、叔丁基甲基醚和乙二醇二甲基醚，环醚如四氢呋喃和二噁烷，烷烃如己烷、庚烷和戊烷，芳香烃溶剂如枯烯，及这些溶剂的混合物。醚是优选的溶剂。
通常，在本发明方法中采用不含氧气的气氛，直至亲电子试剂已经完全与式(Ⅲ)所示的锂代吡啶发生了反应生成式(Ⅰ)所示的2位被取代的吡啶时为止。
本发明方法的步骤(ⅰ)和(ⅱ)可在任何适当的温度下进行，但优选在约-100℃-约25℃的温度下进行。更优选的温度是0℃或0℃以下。在步骤(ⅰ)中，优选的温度为约-78℃-约-30℃，在步骤(ⅱ)中，优选的温度是约-78℃-约0℃。
本发明方法步骤(ⅰ)的反应时间为约5分钟-约12小时，并且该时间在一定程度上取决于反应的大小和反应器的构造。步骤(ⅰ)的反应时间优选为约1-6小时，更优选为约1-4小时。步骤(ⅱ)的反应时间为约1分钟-约2天，且该时间在一定程度上取决于反应的大小和反应器的构造。步骤(ⅱ)的反应时间优选为约1分钟-约12小时，更优选为约1分钟-约4小时。
在步骤(ⅰ)中，将仲丁基锂加入式(Ⅱ)所示化合物中。在步骤(ⅱ)中，可将亲电子试剂加入式(Ⅲ)所示化合物中，也可反过来将式(Ⅲ)所示化合物加入亲电子试剂中。然而，将亲电子试剂加入式(Ⅲ)所示化合物中是优选的。
下面的实施例用于对本发明的进一步说明，并不是用于限制由权利要求所定义的本发明的范围。实施例1
2-乙酰基-5-氯吡啶的制备
给2升的4颈烧瓶装配搅拌器、温度计和250ml的加液漏斗。用氮气过夜吹洗该烧瓶以完成准备工作。将仲丁基锂的1.3M环己烷溶液(222ml,0.289mol)用套管装入加液漏斗中。将2-溴-5-氯吡啶(57.72克，MW=192.4,0.30mol)和600ml乙醚装入烧瓶，然后在丙酮/干冰浴中进行冷却。所得浆料的温度为-76℃。以一定的速率滴加仲丁基锂，将反应温度维持在-74℃或以下。该滴加步骤持续了1.5小时。当滴加结束时，用20ml乙醚冲洗加液漏斗，然后再将30.7ml的N,N-二甲基乙酰胺(MW=87.12,d=0.937,0.330mol)和30ml的乙醚装入该加液漏斗。加入仲丁基锂结束10分钟后，将N,N-二甲基乙酰胺溶液滴加到反应混合物中，同样将反应温度维持在-74℃或以下。此滴加步骤持续了约40分钟。在滴加N,N-二甲基乙酰胺结束后，将反应混合物在-76℃静置1小时，然后移去丙酮/干冰浴并使温度升至-30℃。在该温度下再次换上冷浴，并用200ml 3N HCl终止反应。使反应混合物的温度升至室温，并静置过夜。进行相分离，乙醚相用水和饱和盐水洗涤，然后再用无水MgSO4干燥。弃去乙醚，将粗产物溶解于二氯甲烷中，然后用等重量的硅胶处理。所得浆液用硅藻土过滤并将其全部淋洗下来。产物用己烷进行重结晶，得到29.35g的2-乙酰基-5-氯吡啶(基于所用限制试剂仲丁基锂的量，收率为65％)。
在可比较的另一轮反应中采用类似量的试剂和步骤，但是用正丁基锂代替仲丁基锂，2-乙酰基-5-氯吡啶的收率只达30％。实施例2
2-乙酰基-5-(三氟甲基)吡啶的制备
用氮气吹洗250ml的三颈烧瓶。将4.20g 2-溴-5-(三氟甲基)吡啶溶于50ml无水乙醚而得的溶液冷却至-78℃。滴加仲丁基锂(15.8ml，1.2M)达40分钟，并使反应物温度维持在-72℃或以下。该滴加结束后，使反应混合物静置10分钟，然后加入1.85ml N,N-二甲基乙酰胺溶于1.85ml乙醚而得的溶液，在此期间将温度维持在-74℃或更低。将反应混合物于-78℃静置15分钟，然后移去冷浴，并使温度升至0℃。在该温度下再次换上冷浴，并用20ml 1N HCl终止反应。使反应混合物的温度升至室温，并静置过夜。进行相分离，乙醚相用水和饱和的盐水洗涤，用无水MgSO4干燥，并弃去乙醚。所得产物用柱色谱进行纯化，得到0.4g黄色油状的2-乙酰基-5-(三氟甲基)吡啶(收率为10％)。该产物含有痕量的溶剂和大约5％的杂质。另外，还得到了其它较低纯度的物质。
采用类似的反应条件，但是用正丁基锂代替仲丁基锂，在大致同样规模上的2-溴-5-三氟甲基吡啶(4.52克)的反应没有产出所需的产物。
应该理解的是，本说明书是描述性的并不对本发明构成限制，在不背离本发明精神和由所附权利要求定义的本发明范围的前提下，可对本发明进行各种修改和变化。

Claims (12)

1．式(Ⅰ)所示2位被取代吡啶
Figure A9910598600021
的制备方法，该方法包括如下步骤：(ⅰ)使(Ⅱ)所示2位被取代吡啶与仲丁基锂反应，生成式(Ⅲ)所示的2-锂代吡啶中间体
Figure A9910598600023
(ⅱ)使式(Ⅲ)所示2-锂代吡啶中间体与亲电子试剂反应，生成式(Ⅰ)所示的2-位被取代的吡啶，其中
X是溴或碘，
各式中的Y是在所用反应条件下不与锂化合物反应的基团，
Z是上述亲电子试剂的残基。
2．权利要求1所述的方法，其中各式中的Y独立地选自氢原子、氟、氯、烷基、氟代烷基、三氯甲基、烷氧基、氟代烷氧基、烷硫基、氟代烷硫基、N,N-二烷基碳酰胺、苯基和被一个或多个取代基取代的苯基，所述取代基独立地选自氟、氯、烷基、氟代烷基、烷氧基、氟代烷氧基、烷硫基、氟代烷硫基和N,N-二烷基碳酰胺。
3．权利要求2所述的方法，其中各式中的Y独立地选自氢原子、氟、氯、(C1-C4)烷基、氟代(C1-C4)烷基、(C1-C4)烷氧基、氟代(C1-C4)烷氧基、(C1-C4)烷硫基、氟代(C1-C4)烷硫基、N,N-二(C1-C2)烷基碳酰胺、苯基和被一个或多个取代基取代的苯基，所述取代基独立地选自氟、氯、(C1-C2)烷基、氟代(C1-C2)烷基、(C1-C2)烷氧基、氟代(C1-C2)烷氧基、(C1-C2)烷硫基和氟代(C1-C2)烷硫基。
4．权利要求3所述的方法，其中各式中的Y独立地选自氢原子、氟、氯、甲基、乙基、甲氧基、乙氧基、三氟甲基和三氟甲氧基。
5．权利要求4所述的方法，其中各式中的Y独立地选自氢原子、氟、氯、三氟甲基和三氟甲氧基。
6．权利要求1所述的方法，其中所述亲电子试剂选自烷基碘、溴代烷基烷基醚、碘代烷基烷基醚、醛、酮、N,N-二烷基酰胺、烷基磺酸酯、硼酸酯、烷基二硫化物、芳基二硫化物、腈、氯甲酸烷基酯、二氧化碳、三烷基硅氯、氯化三烷基锡、二氧化硫、磺酰氯和带有正电性卤素原子的物质。
7．权利要求6所述的方法，其中所述亲电子试剂选自碘代甲烷、碘代乙烷、碘代丙烷、溴代甲基甲基醚、碘代乙基乙基醚、甲醛、苯甲醛、二苯甲酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲酰基哌啶、磺酸二甲酯、硼酸三甲酯、硼酸三异丙酯、二甲二硫、二乙化二硫、二硫二苯、乙腈、丙腈、氯甲酸甲酯、氯甲酸乙酯、二氧化碳、三甲基硅氯、氯化三甲基锡、二氧化硫和磺酰氯。
8．权利要求1所述的方法，其中Z是烷基、烷氧基烷基、烷硫基、苯硫基、甲酰基、乙酰基、苯甲酰基、羧基或羧化物、氯代磺酰基、磺基或磺酸酯(盐)、烷氧基羰基、三烷基甲硅烷基、三烷基锡或卤素。
9．权利要求8所述的方法，其中Z是(C1-C6)烷基、(C1-C3)烷氧基(C1-C2)烷基、(C1-C3)烷硫基、苯硫基、甲酰基、乙酰基、苯甲酰基、羧基或羧化物、氯代磺酰基、磺基或磺酸酯(盐)、(C1-C2)烷氧基羰基或三(C1-C4)烷基甲硅烷基。
10．权利要求1所述的方法，其中X为溴。
11．权利要求1所述的方法，还包括使用无水的对质子惰性的溶剂，所述溶剂为醚、环醚、烷烃、芳烃溶剂或这些物质的混合物。
12．权利要求11所述的方法，其中所述溶剂是醚。
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CN102746329A (zh) * 2012-07-02 2012-10-24 盛世泰科生物医药技术(苏州)有限公司 一种4-（1-羟基-1,3二氢-苯并[c][1,2]硼酸-6酚）腈基苯的合成方法
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CN1308331C (zh) * 2000-02-02 2007-04-04 万有制药株式会社 通过卤素－金属交换反应交换官能团的方法
CN102746329A (zh) * 2012-07-02 2012-10-24 盛世泰科生物医药技术(苏州)有限公司 一种4-（1-羟基-1,3二氢-苯并[c][1,2]硼酸-6酚）腈基苯的合成方法
CN111962051A (zh) * 2020-08-21 2020-11-20 广州三孚新材料科技股份有限公司 一种异质结太阳能电池用化学镀铜液及其制备方法

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