CN116396213B - 一种2-吡啶甲酸甲酯的制备方法 - Google Patents
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- NMMIHXMBOZYNET-UHFFFAOYSA-N Methyl picolinate Chemical compound COC(=O)C1=CC=CC=N1 NMMIHXMBOZYNET-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 48
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 23
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 20
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
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- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims description 3
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- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
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- 239000012498 ultrapure water Substances 0.000 claims description 3
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- 230000002194 synthesizing effect Effects 0.000 abstract 1
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- 238000006555 catalytic reaction Methods 0.000 description 3
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- 239000002699 waste material Substances 0.000 description 2
- MLDQJTXFUGDVEO-UHFFFAOYSA-N BAY-43-9006 Chemical compound C1=NC(C(=O)NC)=CC(OC=2C=CC(NC(=O)NC=3C=C(C(Cl)=CC=3)C(F)(F)F)=CC=2)=C1 MLDQJTXFUGDVEO-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- JJKSAEHNIHMQKQ-UHFFFAOYSA-N copper;quinoline Chemical compound [Cu].N1=CC=CC2=CC=CC=C21 JJKSAEHNIHMQKQ-UHFFFAOYSA-N 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- SHNUBALDGXWUJI-UHFFFAOYSA-N pyridin-2-ylmethanol Chemical compound OCC1=CC=CC=N1 SHNUBALDGXWUJI-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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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
- C07D213/79—Acids; Esters
-
- 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
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
本发明公开了一种合成2‑吡啶甲酸甲酯的制备方法，属于化学合成领域。本发明提供一种新型2‑吡啶甲酸甲酯的合成方法是以铜石墨烯复合材料为催化剂，吡啶与氯甲酸甲酯加热反应，并通过萃取等后处理得到2‑吡啶甲酸甲酯。所用的铜石墨烯复合材料由氧化石墨烯和三水合硝酸铜溶液，通过化学还原法将铜和氧化石墨烯还原后经煅烧处理而制得。本发明采用无溶剂合成工艺，具有操作流程简单，催化剂可回收利用，产品提纯方便，得到的产品纯度高的优点。
Description
技术领域
本发明涉及化学合成技术领域，具体涉及一种2-吡啶甲酸甲酯的制备方法。
背景技术
2-吡啶甲酸甲酯，CAS号：2459-07-6，分子量：137.136，密度：1.1g/cm3，沸点：227℃，分子式：C7H7NO2，熔点：18.7℃，是无色至浅黄色透明液体。2-吡啶甲酸甲酯是重要的精细化学品及医药和材料中间体，是制备抗癌药物索拉非尼的重要中间体。
文献中描述以四丁基碘化铵(TBAI)和氟化铜(CuF2)为催化剂，制备了喹啉铜络合物，并将其用作均相铜基催化剂催化甲酯化反应，该工艺操作简单，但使用上述催化剂和TBAI作为添加剂导致产生含铜量的废料，后处理困难，不符合绿色合成。
Senthamarai等人在Chem,8(2),508-531；2022中使用催化剂将2-吡啶甲醇氧化成羧酸并与甲醇反应生成2-吡啶甲酸甲酯，该工艺反应条件温和，催化剂可以循环使用，但生成的产品纯度低，需要柱层析纯化，不适合大规模生产。
Mata,Alejandro等人在Chem Cat Chem,11(3),997-1001；2019中也研究了2-吡啶甲酸甲酯的合成，但是反应中需要应用有毒气体一氧化碳且反应条件需要高温高压，最后得到的产品也需要柱层析纯化，操作繁琐，不利于工艺生产。
石墨烯是一种由碳原子紧密堆积的二维纳米材料，因为它具有非常好的力学、热学、光学和电学性能，使其在复合材料、电化学传感、能量储存和催化领域有着广阔的应用前景。在有机催化领域，石墨烯作为优良的载体，通过水热还原，化学还原，等方法将金属纳米粒子均匀地负载到石墨烯片层上，利用石墨烯和金属纳米粒子之间的协同作用起到了高效的催化作用。
发明内容
本发明针对现有技术上的不足，提出的解决的问题在于提供了一种铜石墨烯复合材料的制备方法，及其催化吡啶与氯甲酸甲酯的加热反应得到2-吡啶甲酸甲酯。为解决上述问题本发明的技术方案为：
以铜石墨烯复合材料为催化剂，催化吡啶与氯甲酸甲酯加热反应，并通过萃取等后处理得到2-吡啶甲酸甲酯。
具体地，所述铜石墨烯复合材料由氧化石墨烯和三水合硝酸铜水溶液通过化学还原后煅烧处理而制得，其制备方法包括以下步骤：
(1)石墨粉置于烧瓶中，并加入浓H2SO4和H3PO4溶液，缓慢加入高锰酸钾，在低温环境下搅拌；升温至40℃并保温12h，将所得产物加入到冰水中，搅拌并加入30％的双氧水至溶液变为金黄色，离心过滤，并用5％HCl溶液和蒸馏水离心洗涤至中性，置于烘箱干燥后研磨，得到氧化石墨烯；
(2)称取制备的氧化石墨烯于超纯水中超声分散后，得到氧化石墨烯悬浮液，将其与三水合硝酸铜水溶液混合后室温搅拌，滴加硼氢化钠溶液，搅拌反应；将得到的悬浮液离心，离心后得到的固体材料放入管式炉中煅烧；自然冷却，用水、乙醇洗涤，得到铜石墨烯复合材料。
具体地，所述的一种2-吡啶甲酸甲酯的制备方法中，其特征在于，氧化石墨烯溶液浓度为3mg/mL，三水合硝酸铜水溶液浓度为0.6mol/L，固体材料在管式炉中煅烧3h。
具体地，所述的一种2-吡啶甲酸甲酯的制备方法中，其特征在于，所用的吡啶与铜石墨烯复合材料的质量比为50～100：1。
具体地，所述的一种2-吡啶甲酸甲酯的制备方法中，其特征在于，所用的吡啶与氯甲酸甲酯的摩尔比为1：1～2.5。
具体地，所述的一种2-吡啶甲酸甲酯的制备方法中，其特征在于，氯甲酸甲酯与吡啶反应的温度为90～110℃。
具体地，所述的一种2-吡啶甲酸甲酯的制备方法中，其特征在于，该反应为无溶剂反应。
本发明有益效果为：
传统反应方法或产生含铜量的废料，后处理困难，不符合绿色合成；或产率低，操作繁琐，不利于工业化生产。本发明反应安全可靠，成本低，且固体催化剂可回收利用，操作简单，得到的产物收率高、纯度高，具有很好的工业放大前景。
具体实施方式
为了进一步了解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
铜石墨烯复合材料制备方法包括以下步骤：
(1)称取2g石墨粉置于烧瓶中，并加入体积比为8:1浓H2SO4和H3PO4溶液，缓慢加入10g高锰酸钾，在低温环境下搅拌1h；升温至40℃并保温12h，将所得产物加入到冰水中，搅拌并加入30％的双氧水至溶液变为金黄色，离心过滤，并用5％HCl溶液和蒸馏水离心洗涤至中性，置于烘箱干燥后研磨，得到氧化石墨烯；
(2)称取氧化石墨烯于超纯水中超声分散后，得到3mg/mL氧化石墨烯悬浮液，将其与三水合硝酸铜(0.725g，0.6mol/mL)水溶液混合后室温搅拌，向混合物中滴加10mL硼氢化钠(0.5mol/L)溶液，30℃搅拌反应；反应结束后，将所得悬浮液进行离心，离心后得到的固体材料放入管式炉中500℃煅烧3h；自然冷却后，用水、乙醇各洗涤材料三次，干燥后得到铜石墨烯复合材料。
本发明产品气相检测条件：柱箱80℃，进样口180℃，检测器220℃，氢气流量30.0mL/min，流量1.0ml/min，梯度80℃～220℃，速率10℃/min。
实施例1
取一100mL三口瓶，量取(10g，1eq)吡啶和(23.81g，2eq)氯甲酸甲酯加入其中，再称取0.02g铜石墨烯复合材料加入其中，加热100℃反应。反应结束后，抽滤催化剂固体，将滤液加入50mL水，并用150mL二氯甲烷分三次萃取，旋蒸有机相，得产品。测气相纯度为99.1％，收率为81.3％。
实施例2
取一100mL三口瓶，量取(10g，1eq)吡啶和(11.96g，1eq)氯甲酸甲酯加入其中，再称取0.02g铜石墨烯复合材料加入其中，加热100℃反应。反应结束后，抽滤催化剂固体，将滤液加入50mL水，并用150mL二氯甲烷分三次萃取，旋蒸有机相，得产品。测气相纯度为98.5％，收率为75.3％。
实施例3
取一100mL三口瓶，量取(10g，1eq)吡啶和(17.86g，1.5eq)氯甲酸甲酯加入其中，再称取0.02g铜石墨烯复合材料加入其中，加热100℃反应。反应结束后，抽滤催化剂固体，将滤液加入50mL水，并用150mL二氯甲烷分三次萃取，旋蒸有机相，得产品。测气相纯度为98.9％，收率为78.4％。
实施例4
取一100mL三口瓶，量取(10g，1eq)吡啶和(29.76g，2.5eq)氯甲酸甲酯加入其中，再称取0.02g铜石墨烯复合材料加入其中，加热100℃反应。反应结束后，抽滤催化剂固体，将滤液加入50mL水，并用150mL二氯甲烷分三次萃取，旋蒸有机相，得产品。测气相纯度为98.7％，收率为80.15％。
实施例5
取一100mL三口瓶，量取(10g，1eq)吡啶和(23.81g，2eq)氯甲酸甲酯加入其中，再称取0.015g铜石墨烯复合材料加入其中，加热100℃反应。反应结束后，抽滤催化剂固体，将滤液加入50mL水，并用150mL二氯甲烷分三次萃取，旋蒸有机相，得产品。收率为78.5％，测气相纯度为98.8％，。
实施例6
取一100mL三口瓶，量取(10g，1eq)吡啶和(23.81g，2eq)氯甲酸甲酯加入其中，再称取0.01g铜石墨烯复合材料加入其中，加热100℃反应。反应结束后，抽滤催化剂固体，将滤液加入50mL水，并用150mL二氯甲烷分三次萃取，旋蒸有机相，得产品。测气相纯度为98.8％，收率为76.4％。
实施例7
取一100mL三口瓶，量取(10g，1eq)吡啶和(23.81g，2eq)氯甲酸甲酯加入其中，再称取0.02g铜石墨烯复合材料加入其中，加热90℃反应。反应结束后，抽滤催化剂固体，将滤液加入50mL水，并用150mL二氯甲烷分三次萃取，旋蒸有机相，得产品。测气相纯度为98.9％，收率为77.9％。
实施例8
取一100mL三口瓶，量取(10g，1eq)吡啶和(23.81g，2eq)氯甲酸甲酯加入其中，再称取0.02g铜石墨烯复合材料加入其中，加热110℃反应。反应结束后，抽滤催化剂固体，将滤液加入50mL水，并用150mL二氯甲烷分三次萃取，旋蒸有机相，得产品。测气相纯度为98.7％，收率为80.5％。
对比实施例1
取一100mL三口瓶，量取(10g，1eq)吡啶和(23.81g，2eq)氯甲酸甲酯加入其中，加热110℃反应。反应结束后，将滤液加入50mL水，并用150mL二氯甲烷分三次萃取，旋蒸有机相，得产品。测气相纯度为74.3％，收率为24.8％。
对比实施例2
取一100mL三口瓶，量取(10g，1eq)吡啶和(23.81g，2eq)氯甲酸甲酯加入其中，再称取0.02gAlCl3加入其中，加热110℃反应。反应结束后，抽滤催化剂固体，将滤液加入50mL水，并用150mL二氯甲烷分三次萃取，旋蒸有机相，得产品。测气相纯度为84.2％，收率为51.4％。
上述虽然结合实施例对本发明的具体实施方式进行了描述，但并非对本发明实施方式的限定。对所属领域技术人员来说，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。
Claims (6)
1.一种2-吡啶甲酸甲酯的制备方法，其特征在于，所述制备方法为：以铜石墨烯复合材料为催化剂，吡啶与氯甲酸甲酯在加热条件下反应，萃取、纯化得到2-吡啶甲酸甲酯，所述铜石墨烯复合材料是由氧化石墨烯和铜盐溶液通过化学还原后经煅烧、洗涤处理而制得，具体铜石墨烯复合材料制备方法包括以下步骤：
(1)石墨粉置于烧瓶中，加入浓H 2SO 4和H 3PO 4溶液，缓慢加入高锰酸钾，在低温环境下搅拌；升温至40℃并保温12h，将所得产物加入到冰水中，搅拌并加入30％的双氧水至溶液变为金黄色，离心过滤，并用5％HCl溶液和蒸馏水离心洗涤至中性，置于烘箱干燥后研磨，得到氧化石墨烯；
(2)称取由制备的氧化石墨烯于超纯水中超声分散后，得到氧化石墨烯悬浮液，将其与三水合硝酸铜水溶液混合后室温搅拌，滴加硼氢化钠溶液，搅拌反应；将得到的悬浮液离心，离心后得到的固体材料放入管式炉中煅烧；自然冷却，用水、乙醇洗涤，得到铜石墨烯复合材料。
2.如权利要求1所述的一种2-吡啶甲酸甲酯的制备方法中，其特征在于，吡啶与铜石墨烯复合材料的质量比为50～100：1。
3.如权利要求1所述的一种2-吡啶甲酸甲酯的制备方法中，其特征在于，吡啶与氯甲酸甲酯的摩尔比为1：1～2.5。
4.如权利要求1所述的一种2-吡啶甲酸甲酯的制备方法中，其特征在于，氯甲酸甲酯与吡啶反应温度为90～110℃。
5.如权利要求1所述的一种2-吡啶甲酸甲酯的制备方法中，其特征在于，该反应为无溶剂反应。
6.如权利要求1所述的一种2-吡啶甲酸甲酯的制备方法中，其特征在于，氧化石墨烯悬浮液浓度为3mg/mL，三水合硝酸铜水溶液浓度为0.6mol/L，固体材料在管式炉中煅烧3h。
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