CN106008329A - 一种制备5-氯-2,3-二氟吡啶的方法 - Google Patents

一种制备5-氯-2,3-二氟吡啶的方法 Download PDF

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CN106008329A
CN106008329A CN201610151939.7A CN201610151939A CN106008329A CN 106008329 A CN106008329 A CN 106008329A CN 201610151939 A CN201610151939 A CN 201610151939A CN 106008329 A CN106008329 A CN 106008329A
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trichloropyridine
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王法强
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Dimension Chemical (nanjing) Co Ltd
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Dimension Chemical (nanjing) Co Ltd
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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

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Abstract

本发明公开了一种制备5-氯-2,3-二氟吡啶的方法，采用2-氨基吡啶为起始原料，将其氯化生成2-氨基- 3,5-二氯吡啶，然后重氮化后，发生桑德迈尔反应生成2,3,5-三氯吡啶和3,5-二氯吡啶-2-酮的混合物，再次氯化，经处理得到2,3,5-三氯吡啶；最后以制得的2,3,5-三氯吡啶为原料，用环丁砜和二甲亚砜为溶剂，加入氟化铯和氟化钾的混合物作为氟化剂，反应温度控制在145℃，保温17h，之后升温至190℃，保温19h，上述制备工艺及操作实用性强，步骤简单，对设备要求不高，适合工业化生产，产品收率达到90%、含量达到99.8%。

Description

一种制备 5- 氯 -2,3- 二氟吡啶的方法
技术领域
本发明涉及一种制备吡啶的方法，具体涉及一种制备5-氯-2,3-二氟吡啶的方法。
背景技术
近十年来含氟农药得到迅速发展，已经成为世界农药工业发展的重点，其中开发与应用较多的有含氟拟除虫菊酯类与含氟苯甲酰脲类杀虫剂。因为氟原子半径小，略大于氢原子半径，具有极大的电负性，接近于羟基，其所形成的c－F键能比c－H键能要大，能使氟化物保持高的稳定性；又由于氟原子(尤其是cF基)的引入，使分子内电子云密度降低，提高了抗分解的能力，从而使化合物表现出持久效能；同时，氟原子或含氟基团的引入，能提高化合物的脂溶性，即增强疏水性，易于渗透生物膜而迅速达到作用部位，与生物体内的酶结合，使之受到抑制，从而使生物体丧失机能而致死亡。所以氟原子和含氟基团(如三氟甲基、三氟甲氧基、二氟甲基、二氟甲氧基)代替农药芳环上的其它基团，能够显著的提高农药的活性，含氟农药的生物活性往往能比其对应的非氟农药增大数倍。很多含氟农药在性能上相对具有用量少、毒性低、药效高、代谢能力强等特点，这使它在新农药品种中所占比例越来越高。
发明内容
针对上述存在的技术问题，本发明的目的是：提出了一种制备4,4’-二氟二苯甲酮的方法，制备工艺简单，适宜于工业化生产，且产品收率达到90%、含量达到96.8%。
本发明的技术解决方案是这样实现的：一种制备5-氯-2,3-二氟吡啶的方法，采用2-氨基吡啶为起始原料；首先通过对2-氨基吡啶的氯化生成2-氨基- 3,5-二氯吡啶，然后再有盐酸存在条件下加亚硝酸钠溶液重氮化后，发生桑德迈尔反应生成2,3,5-三氯吡啶和3,5-二氯吡啶-2-酮的混合物，然后用氯化亚砜进行再次氯化，经处理得到2,3,5-三氯吡啶；最后以制得的2,3,5-三氯吡啶为原料，用环丁砜和二甲亚砜为溶剂，加入氟化铯和氟化钾的混合物作为氟化剂，反应温度控制在145℃，保温17h，之后升温至190℃，保温19h，连续移出产物，可以得到所需的产品2,3-二氟-5-氯吡啶，收率为90％，产品纯度为96.8％。
优选的，所述2,3,5－三氯吡啶与氟化钾的摩尔比为1:2.5。
由于上述技术方案的运用，本发明与现有技术相比具有下列优点：
本发明的制备5-氯-2,3-二氟吡啶的方法，工艺及操作实用性强，步骤简单，对设备要求不高，适合工业化生产，产品收率达到90%以上、含量达到99.8%以上。
具体实施方式
本发明所述的一种制备5-氯-2,3-二氟吡啶的方法，采用2-氨基吡啶为起始原料；首先通过对2-氨基吡啶的氯化生成2-氨基- 3,5-二氯吡啶，然后再有盐酸存在条件下加亚硝酸钠溶液重氮化后，发生桑德迈尔反应生成2,3,5-三氯吡啶和3,5-二氯吡啶-2-酮的混合物，然后用氯化亚砜进行再次氯化，经处理得到2,3,5-三氯吡啶；最后以制得的2,3,5-三氯吡啶为原料，用环丁砜和二甲亚砜为溶剂，加入氟化铯和氟化钾的混合物作为氟化剂，反应温度控制在145℃，保温17h，之后升温至190℃，保温19h，催化效果好，连续移出产物，可以得到所需的产品2,3-二氟-5-氯吡啶。
安装好减压蒸镏装置，称取400g环丁砜和400g二甲亚砜快速加到1000mL烧瓶中，在200℃，0.07 MPa(负压)脱水到0.05％以下；称取96g(1.66mol) 氟化铯，96g(1.66mol)氟化钾，120g(0.67mol)三氯吡啶，2g18-冠醚，3g碳酸钾于120度加入反应瓶中，升温至200度保温3h；升温，通入氮气鼓泡，约3h收集完产物；得产物95g(0.51mol)，收率90％；通过气相色谱测得纯度96.8％。
红外光谱图图谱分析数据：3078.2cm是c:c-H的伸缩振动，1598.3，1470.3cm分别是C:C、C=N的伸缩振动，1173.3，1245.0，1419.1cm是C．F伸缩振动，927.5，896.7，794.3，732.9cm是c=c-H的弯曲振动和C-C1的伸缩振动，符合5-氯-2,3-二氟吡啶的结构。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并加以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围内。

Claims (2)

1.一种制备5-氯-2,3-二氟吡啶的方法，其特征在于: 采用2-氨基吡啶为起始原料；首先通过对2-氨基吡啶的氯化生成2-氨基- 3,5-二氯吡啶，然后再有盐酸存在条件下加亚硝酸钠溶液重氮化后，发生桑德迈尔反应生成2,3,5-三氯吡啶和3,5-二氯吡啶-2-酮的混合物，然后用氯化亚砜进行再次氯化，经处理得到2,3,5-三氯吡啶；最后以制得的2,3,5-三氯吡啶为原料，用环丁砜和二甲亚砜为溶剂，加入氟化铯和氟化钾的混合物作为氟化剂，反应温度控制在145℃，保温17h，之后升温至190℃，保温19h，连续移出产物，可以得到所需的产品2,3-二氟-5-氯吡啶，收率为90％，产品纯度为96.8％。
2.根据权利要求1所述的制备5-氯-2,3-二氟吡啶的方法，其特征在于:所述2,3,5－三氯吡啶与氟化钾的摩尔比为1:2.5。
CN201610151939.7A 2016-03-17 2016-03-17 一种制备5-氯-2,3-二氟吡啶的方法 Pending CN106008329A (zh)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111592499A (zh) * 2020-06-29 2020-08-28 中山奕安泰医药科技有限公司 法匹拉韦的制备方法
CN111909079A (zh) * 2020-09-04 2020-11-10 利尔化学股份有限公司 一种毒莠定固渣的资源化处理方法
CN115108971A (zh) * 2022-06-30 2022-09-27 杭州凯氟科技有限公司 一种2,3-二氟-5-氯吡啶的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4822887A (en) * 1983-12-23 1989-04-18 The Dow Chemical Company Preparation of difluoropyridine compounds
CN1830963A (zh) * 2005-03-09 2006-09-13 温州师范学院 2，3－二氟－5－氯吡啶的合成方法
CN101648904A (zh) * 2009-09-14 2010-02-17 南京第一农药集团有限公司 一种2,3-二氟-5-氯吡啶的合成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4822887A (en) * 1983-12-23 1989-04-18 The Dow Chemical Company Preparation of difluoropyridine compounds
CN1830963A (zh) * 2005-03-09 2006-09-13 温州师范学院 2，3－二氟－5－氯吡啶的合成方法
CN101648904A (zh) * 2009-09-14 2010-02-17 南京第一农药集团有限公司 一种2,3-二氟-5-氯吡啶的合成方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
杨祥宇: "2,3,5-三氯吡啶及 2,3-二氟-5-氯吡啶的合成研究", 《天津大学硕士学位论文》 *
柳翠英，等: "席夫碱-取代水杨醛缩氨基吡啶衍生物的合成与表征", 《化学试剂》 *
郑静，等: "2,3-二氟-5-氯吡啶的合成", 《化学世界》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111592499A (zh) * 2020-06-29 2020-08-28 中山奕安泰医药科技有限公司 法匹拉韦的制备方法
CN111909079A (zh) * 2020-09-04 2020-11-10 利尔化学股份有限公司 一种毒莠定固渣的资源化处理方法
CN111909079B (zh) * 2020-09-04 2022-05-27 利尔化学股份有限公司 一种毒莠定固渣的资源化处理方法
CN115108971A (zh) * 2022-06-30 2022-09-27 杭州凯氟科技有限公司 一种2,3-二氟-5-氯吡啶的制备方法

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