CN115448851B - 一种卤代芳香基直接合成酰胺类化合物的方法 - Google Patents
一种卤代芳香基直接合成酰胺类化合物的方法 Download PDFInfo
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- -1 amide compound Chemical class 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- ARHOUOIHKWELMD-UHFFFAOYSA-N 1-ethenyl-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C=C)=C1 ARHOUOIHKWELMD-UHFFFAOYSA-N 0.000 claims description 2
- VLJIVLGVKMTBOD-UHFFFAOYSA-N 2-chloro-5-(trichloromethyl)pyridine Chemical compound ClC1=CC=C(C(Cl)(Cl)Cl)C=N1 VLJIVLGVKMTBOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 3
- 238000007789 sealing Methods 0.000 claims 2
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 claims 1
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- IDOKWIROLYYEIB-UHFFFAOYSA-N [I].[Br].[Cl].[F] Chemical compound [I].[Br].[Cl].[F] IDOKWIROLYYEIB-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000005480 nicotinamides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/08—Preparation of carboxylic acid amides from amides by reaction at nitrogen atoms of carboxamide groups
-
- 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
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明提供了一种卤代芳香基直接合成酰胺类化合物的方法,包括以下步骤:S1、将DMF和卤代芳香类化合物融入有机溶剂中进行反应;S2、加入强碱,实现碳卤键的断裂以及碳氧双键以及酰胺键的构建,得到相应的酰胺类化合物。本发明的优点在于:条件温和、操作简单、绿色高效、适合大规模生产。
Description
技术领域
本发明涉及酰胺键形成方法技术领域,特别涉及一种卤代芳香基直接合成酰胺类化合物的方法。
背景技术
酰胺类化合物是一种重要的有机化合物,具有重要的药用价值和应用前景,广泛应用于化学、医药、材料、农业科学等领域,他的合成日益引起有机化学家的兴趣,已经发展出四十余种合成酰胺类化合物的方法。酰胺类化合物广泛应用于杀虫剂,杀菌剂,除草剂,烟酰胺类化合物应用于化妆品,维生素,药物合成等领域,在蛋白质生物合成领域也有广泛应用,酰胺键的合成具有重要研究意义。这些方法都有较大的局限性,如温度高,时间长,适用性低,产率较低,需要金属催化剂等。因此,需要一种条件温和、操作简单、适合大规模生产的酰胺键的生成方法。
发明内容
为了解决上述问题,本发明提供了一种条件温和、操作简单、绿色高效、适合大规模生产的卤代芳香基直接合成酰胺类化合物的方法。
为了达到上述目的,本发明一种卤代芳香基直接合成酰胺类化合物的方法,包括以下步骤:
S1、将DMF和卤代芳香类化合物融入有机溶剂中进行反应;
S2、加入强碱,实现碳卤键的断裂以及碳氧双键以及酰胺键的构建,得到相应的酰胺类化合物。
具体地,所述的有机溶剂采用DMF、DMSO、二氯甲烷、乙醇、四氢呋喃、一四二氧六环中的一种和水的混合物。
具体地,所述有机溶剂为水和DMF混合溶液。
具体地,所述S1中的反应的温度为0-150℃。
具体地,所述的卤代芳香类化合物采用三氯甲基芳香烃、三氟甲基芳香烃、三溴甲基芳香烃、三碘甲基芳香烃中的一种。
具体地,所述卤代芳香类化合物采用三氯甲基芳香烃。
具体地,所述强碱采用氢氧化钾、氢氧化钠、叔丁醇钾、叔丁醇锂中的一种。
具体地,所述强碱采用氢氧化钾。
具体地,所述酰胺类化合物为DMF、N,N二乙基甲酰胺、N,N二甲基乙酰胺、N-甲基甲酰苯胺具有酰胺键的化合物。
具体地,所述酰胺类化合物为DMF。
本发明的上述方案有如下的有益效果:
1、条件简单,只需要加入强碱即可完成反应;
2、绿色高效,可以在水溶剂中进行,并且产率在90%以上;
3、操作简单,一步完成,并且不需要后处理,萃取旋蒸之后使用真空泵抽2h即可得到纯品;
4、底物适用性广,卤素可以选择氟氯溴碘,并且酰胺类化合物选择也比较多。
附图说明
图1是本发明的反应式。
具体实施方式
为使本发明要解决的技术问题、技术方案和优点更加清楚,下面将结合附图及具体实施例进行详细描述。
结合附图1,其中R1、R2为任意的有机侧链或者H,如烷烃侧链或脂肪侧链等。X为任意卤素,如氟、氯、溴、碘等。
实施例1
称取224mg氢氧化钾固体加入到10ml反应管中,再称取0.5mmol三氯甲苯于1ml离心管用1ml DMF溶液溶解后使用1ml针管转移到反应管中,使用1ml针管反应管中加入1ml去离子水密封反应管。于30度条件下反应12h,反应液用二氯甲烷和饱和食盐水萃取三遍,无水硫酸钠干燥,浓缩,使用真空油泵抽真空2h即可得到纯品酰胺类化合物,产率90%。
实施例2
称取224mg氢氧化钾固体加入到10ml反应管中,再称取0.5mmol 2-氯-5-三氯甲基吡啶于1ml离心管用1ml DMF溶液溶解后使用1ml针管转移到反应管中,使用1ml针管反应管中加入1ml去离子水密封反应管。于30度条件下反应12h,反应液用二氯甲烷和饱和食盐水萃取三遍,无水硫酸钠干燥,浓缩,使用真空油泵抽真空2h即可得到纯品酰胺类化合物,产率90%。
实施例3
称取224mg氢氧化钾固体加入到10ml反应管中,再称取0.5mmol 3-(三氟甲基)苯乙烯于1ml离心管用1ml DMF溶液溶解后使用1ml针管转移到反应管中,使用1ml针管反应管中加入1ml去离子水密封反应管。于30度条件下反应12h,反应液用二氯甲烷和饱和食盐水萃取三遍,无水硫酸钠干燥,浓缩,使用真空油泵抽真空2h即可得到纯品酰胺类化合物,产率90%。
以上实施例仅用以说明而非限制本发明的技术方案,尽管参照上述实施例对本发明进行了详细说明,本领域的普通技术人员应当理解:依然可以对本发明进行修改或者等同替换,而不脱离本发明的精神和范围的任何修改或局部替换,其均应涵盖在本发明的权利要求范围当中。
Claims (3)
1.一种酰胺类化合物的合成方法,其特征在于,称取224mg氢氧化钾固体加入到10ml反应管中,再称取0 .5mmol三氯甲苯于1ml离心管用1ml DMF溶液溶解后使用1ml针管转移到反应管中,使用1ml针管反应管中加入1ml去离子水密封反应管;于30度条件下反应12h,反应液用二氯甲烷和饱和食盐水萃取三遍,无水硫酸钠干燥,浓缩,使用真空油泵抽真空2h即可得到纯品酰胺类化合物。
2.一种酰胺类化合物的合成方法,其特征在于,称取224mg氢氧化钾固体加入到10ml反应管中,再称取0 .5mmol 2-氯-5-三氯甲基吡啶于1ml离心管用1ml DMF溶液溶解后使用1ml针管转移到反应管中,使用1ml针管反应管中加入1ml去离子水密封反应管;于30度条件下反应12h,反应液用二氯甲烷和饱和食盐水萃取三遍,无水硫酸钠干燥,浓缩,使用真空油泵抽真空2h即可得到纯品酰胺类化合物。
3.一种酰胺类化合物的合成方法,其特征在于,称取224mg氢氧化钾固体加入到10ml反应管中,再称取0 .5mmol 3-(三氟甲基)苯乙烯于1ml离心管用1ml DMF溶液溶解后使用1ml针管转移到反应管中,使用1ml针管反应管中加入1ml去离子水密封反应管;于30度条件下反应12h,反应液用二氯甲烷和饱和食盐水萃取三遍,无水硫酸钠干燥,浓缩,使用真空油泵抽真空2h即可得到纯品酰胺类化合物。
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JP2013067576A (ja) * | 2011-09-21 | 2013-04-18 | Jx Nippon Oil & Energy Corp | アミド化合物の製造方法とその触媒 |
CN113912509A (zh) * | 2021-10-15 | 2022-01-11 | 武汉理工大学 | 酰胺类化合物的制备方法 |
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JP2013067576A (ja) * | 2011-09-21 | 2013-04-18 | Jx Nippon Oil & Energy Corp | アミド化合物の製造方法とその触媒 |
CN113912509A (zh) * | 2021-10-15 | 2022-01-11 | 武汉理工大学 | 酰胺类化合物的制备方法 |
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Title |
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"KOH-promoted cascade C–Cl bond activation and amidation of trichloromethyl aromatic compounds with formamides in water";Chenyu Wang et al;《Organic & Biomolecular Chemistry》;第第21卷卷(第第25期期);第5185–5188页 * |
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