CN111704575B - Synthesis method of quinoline-2-thiocarboxamide compound under conditions of no catalyst and no additive - Google Patents
Synthesis method of quinoline-2-thiocarboxamide compound under conditions of no catalyst and no additive Download PDFInfo
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- CN111704575B CN111704575B CN202010653476.0A CN202010653476A CN111704575B CN 111704575 B CN111704575 B CN 111704575B CN 202010653476 A CN202010653476 A CN 202010653476A CN 111704575 B CN111704575 B CN 111704575B
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- quinoline
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- -1 quinoline-2-thiocarboxamide compound Chemical class 0.000 title claims abstract description 23
- 239000000654 additive Substances 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- 230000000996 additive effect Effects 0.000 title claims abstract description 12
- 238000001308 synthesis method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- HDDAGABOUKEMAG-UHFFFAOYSA-N quinoline-2-carbothioamide Chemical class C1=CC=CC2=NC(C(=S)N)=CC=C21 HDDAGABOUKEMAG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 46
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000004440 column chromatography Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 7
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- NOYASZMZIBFFNZ-UHFFFAOYSA-N (2-bromophenyl)methanamine Chemical compound NCC1=CC=CC=C1Br NOYASZMZIBFFNZ-UHFFFAOYSA-N 0.000 claims description 3
- CJAAPVQEZPAQNI-UHFFFAOYSA-N (2-methylphenyl)methanamine Chemical compound CC1=CC=CC=C1CN CJAAPVQEZPAQNI-UHFFFAOYSA-N 0.000 claims description 3
- SUYJXERPRICYRX-UHFFFAOYSA-N (3-bromophenyl)methanamine Chemical compound NCC1=CC=CC(Br)=C1 SUYJXERPRICYRX-UHFFFAOYSA-N 0.000 claims description 3
- HMTSWYPNXFHGEP-UHFFFAOYSA-N (4-methylphenyl)methanamine Chemical compound CC1=CC=C(CN)C=C1 HMTSWYPNXFHGEP-UHFFFAOYSA-N 0.000 claims description 3
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 claims description 3
- NVSYANRBXPURRQ-UHFFFAOYSA-N naphthalen-1-ylmethanamine Chemical compound C1=CC=C2C(CN)=CC=CC2=C1 NVSYANRBXPURRQ-UHFFFAOYSA-N 0.000 claims description 3
- DGSRAILDFBJNQI-UHFFFAOYSA-N (2,4,6-trimethylphenyl)methanamine Chemical compound CC1=CC(C)=C(CN)C(C)=C1 DGSRAILDFBJNQI-UHFFFAOYSA-N 0.000 claims description 2
- GBSUVYGVEQDZPG-UHFFFAOYSA-N (2,4-dimethylphenyl)methanamine Chemical compound CC1=CC=C(CN)C(C)=C1 GBSUVYGVEQDZPG-UHFFFAOYSA-N 0.000 claims description 2
- KDDNKZCVYQDGKE-UHFFFAOYSA-N (2-chlorophenyl)methanamine Chemical compound NCC1=CC=CC=C1Cl KDDNKZCVYQDGKE-UHFFFAOYSA-N 0.000 claims description 2
- YMVFJGSXZNNUDW-UHFFFAOYSA-N (4-chlorophenyl)methanamine Chemical compound NCC1=CC=C(Cl)C=C1 YMVFJGSXZNNUDW-UHFFFAOYSA-N 0.000 claims description 2
- IIFVWLUQBAIPMJ-UHFFFAOYSA-N (4-fluorophenyl)methanamine Chemical compound NCC1=CC=C(F)C=C1 IIFVWLUQBAIPMJ-UHFFFAOYSA-N 0.000 claims description 2
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- DHVHORCFFOSRBP-UHFFFAOYSA-N [3,5-bis(trifluoromethyl)phenyl]methanamine Chemical compound NCC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 DHVHORCFFOSRBP-UHFFFAOYSA-N 0.000 claims description 2
- YKNZTUQUXUXTLE-UHFFFAOYSA-N [3-(trifluoromethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(C(F)(F)F)=C1 YKNZTUQUXUXTLE-UHFFFAOYSA-N 0.000 claims description 2
- PRDBLLIPPDOICK-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl]methanamine Chemical compound NCC1=CC=C(C(F)(F)F)C=C1 PRDBLLIPPDOICK-UHFFFAOYSA-N 0.000 claims description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 7
- 150000004982 aromatic amines Chemical class 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001228 spectrum Methods 0.000 description 24
- 229910052739 hydrogen Inorganic materials 0.000 description 23
- 239000001257 hydrogen Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 22
- 229910052799 carbon Inorganic materials 0.000 description 22
- 238000004809 thin layer chromatography Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 238000011221 initial treatment Methods 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000012044 organic layer Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000007858 starting material Substances 0.000 description 11
- 238000006073 displacement reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000003556 thioamides Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- PDHGIVRQQZJDAA-UHFFFAOYSA-N (2,4,5-trimethylphenyl)methanamine Chemical compound CC1=CC(C)=C(CN)C=C1C PDHGIVRQQZJDAA-UHFFFAOYSA-N 0.000 description 1
- QOWBXWFYRXSBAS-UHFFFAOYSA-N (2,4-dimethoxyphenyl)methanamine Chemical compound COC1=CC=C(CN)C(OC)=C1 QOWBXWFYRXSBAS-UHFFFAOYSA-N 0.000 description 1
- WGTASENVNYJZBK-UHFFFAOYSA-N 3,4,5-trimethoxyamphetamine Chemical compound COC1=CC(CC(C)N)=CC(OC)=C1OC WGTASENVNYJZBK-UHFFFAOYSA-N 0.000 description 1
- LYUQWQRTDLVQGA-UHFFFAOYSA-N 3-phenylpropylamine Chemical compound NCCCC1=CC=CC=C1 LYUQWQRTDLVQGA-UHFFFAOYSA-N 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- DBGROTRFYBSUTR-UHFFFAOYSA-N [4-(trifluoromethoxy)phenyl]methanamine Chemical compound NCC1=CC=C(OC(F)(F)F)C=C1 DBGROTRFYBSUTR-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
- Quinoline Compounds (AREA)
Abstract
The invention discloses a synthesis method of quinoline-2-thiocarboxamide compounds under the conditions of no catalyst and no additive. The synthesis method comprises the following steps: adding 2-methylquinoline, aromatic amine or fatty amine compound, sulfur source and solvent into a reaction tube, stirring and reacting at 130-150 ℃, cooling to room temperature after the reaction is finished, and separating and purifying the product to obtain the quinoline-2-thiocarboxamide compound. The invention provides a method for synthesizing a quinoline-2-thiocarboxamide compound without a catalyst and an additive. The reaction condition is simple, raw materials are easy to obtain, the substrate adaptability is good, and a simple, green and efficient synthesis method is provided for synthesizing the quinoline-2-thiocarboxamide compound.
Description
Technical Field
The invention belongs to the field of quinoline-2-thiocarboxamide compounds, and particularly relates to a synthesis method of a quinoline-2-thiocarboxamide compound under the conditions of no catalyst and no additive.
Background
Amide compounds are widely used in the pesticide field, but their poor water solubility limits their development and application. With the continuous progress of research, thioamide compounds are found to replace known amide pesticides (Wang Yanjun, zhang Dayong, wu Xiaoming, pesticides, 2010, 49, 170.), so that agricultural production is more environment-friendly. In addition to their role in the pharmaceutical field, thioamides are also often used as synthons in organic synthesis for the synthesis of various sulfur-or nitrogen-containing heterocyclic organic compounds due to their excellent reactivity. The method for synthesizing thioamides generally selects amides or amines as substrates, and requires metal catalysts or additives, which increases the waste emissions and causes problems of product metal residues (ab Charette, M Grenon, j. Org. Chem., 2003, 68, 5792; K Xu, Z Y Li, F Y Cheng, org. Lett., 2018, 20, 2228; Y Sun, H F Jiang, W Q Wu, org. Biomol. Chem., 2014, 12, 700.). Therefore, it is of great importance to find a method for synthesizing such compounds which uses reagents with low toxicity, which are convenient, safe and easy to obtain, and which is easy to develop, green and efficient.
The invention provides a method for synthesizing quinoline-2-thiocarboxamide compounds by taking 2-methylquinoline, aromatic amine or aliphatic amine as a substrate without catalyst or additive. The reaction condition is simple, raw materials are easy to obtain, the substrate adaptability is good, and a simple, green and efficient synthesis method is provided for synthesizing the quinoline-2-thiocarboxamide compound.
Disclosure of Invention
The invention aims at overcoming the defects and shortcomings of the prior art and provides a method for synthesizing quinoline-2-thiocarboxamide compounds under the conditions of no catalyst and no additive. The reaction does not need a catalyst or an additive, has simple reaction conditions, easily obtained raw materials and better substrate adaptability, and provides a simple, green and efficient synthesis method for synthesizing the quinoline-2-thiocarboxamide compound.
The aim of the invention is achieved by the following technical scheme.
A method for synthesizing quinoline-2-thiocarboxamide compounds under the conditions of no catalyst and no additive comprises the following steps: and adding 2-methylquinoline, aromatic amine or aliphatic amine, a sulfur source and a solvent into a reaction tube, stirring the mixture at 130-150 ℃ for reaction, cooling the mixture to room temperature after the reaction is finished, and separating and purifying a product to obtain the quinoline-2-thiocarboxamide compound.
Further, the chemical reaction equation of the synthesis process is as follows:
wherein R is 1 One selected from hydrogen, methyl and halogen radicals; r is R 2 Is selected from alkyl.
Further, the aromatic amine compound is selected from: aniline, 2-chloroaniline, 3-methylaniline, 4-methylaniline, benzidine. The fatty amine compound is selected from the group consisting of: benzylamine, 4- (trifluoromethyl) benzylamine, 4-fluorobenzylamine, 4-chlorobenzylamine, 4-methylbenzylamine, 4- (trifluoromethoxy) benzylamine, 3-bromobenzylamine, 3- (trifluoromethyl) benzylamine, 2-methylbenzylamine, 2-chlorobenzylamine, 2-bromobenzylamine, 3, 5-bis (trifluoromethyl) benzylamine, 2, 4-dimethylbenzylamine, 2,4, 6-trimethylbenzylamine, 2-pyridinemethylamine, 1-naphthylmethylamine, phenethylamine, cyclohexylamine, cyclopropylamine, cyclopentylamine, 3-phenyl-1-propylamine.
Further, the molar ratio of the addition amount of the aromatic amine or the aliphatic amine compound to the 2-methylquinoline is 1.2-3:1, preferably 2:1.
Further, the sulfur source is elemental sulfur; the molar ratio of the sulfur source to the aniline compound is 2-4:1, preferably 3:1.
Further, the solvent is dimethyl sulfoxide.
Further, the stirring temperature is 130-150 ℃, preferably 140 ℃.
Further, the stirring reaction time is 9 to 15 hours, preferably 11 hours.
Further, the separation and purification operations are as follows: extracting the reaction liquid with ethyl acetate, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, evaporating the organic solvent under reduced pressure to obtain a crude product, and purifying by column chromatography to obtain the quinoline-2-thiocarboxamide compound.
Compared with the prior art, the invention has the following advantages:
the invention provides a synthesis method of quinoline-2-thiocarboxamide compounds under the conditions of no catalyst and no additive. From the green chemical point of view, the invention synthesizes the quinoline-2-thiocarboxamide compound by taking the easily obtained 2-methylquinoline, aromatic amine or fatty amine compound as a substrate and taking the elemental sulfur as a sulfur source under the conditions of no metal catalyst and no additive. The reaction condition is simple, raw materials are easy to obtain, the substrate adaptability is good, and a simple, green and efficient synthesis method is provided for synthesizing the quinoline-2-thiocarboxamide compound.
Drawings
FIGS. 1 and 2 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 1.
Fig. 3 and 4 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 2.
Fig. 5 and 6 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 3.
Fig. 7 and 8 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 4.
Fig. 9 and 10 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 5.
Fig. 11 and 12 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 6.
Fig. 13 and 14 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 7.
Fig. 15 and 16 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 8.
Fig. 17 and 18 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 9.
Fig. 19 and 20 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 10.
Fig. 21 and 22 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 11.
Detailed description of the preferred embodiments
The technical scheme of the present invention is described in further detail below with reference to specific examples and drawings, but the scope and embodiments of the present invention are not limited thereto.
Example 1
2-methylquinoline (0.2 mmol), aniline (0.4 mmol), elemental sulfur (0.6 mmol) and solvent DMSO (2 mL) were sequentially added to a dry Schlenk reaction tube, after the sample was added, the sample was evacuated by an oil pump, then nitrogen was injected to perform gas displacement, after three times of displacement, the reaction was stopped at 140℃for 11 hours, and the reaction was cooled to room temperature. The reaction was checked by Thin Layer Chromatography (TLC) and, after the starting material had reacted, the reaction was terminated and the mixture in the reaction tube was cooled to room temperature. And (3) carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, rotating powder, and performing column chromatography separation and purification to obtain a target product with the yield of 80%.
The hydrogen spectrogram and the carbon spectrogram of the target product are respectively shown in fig. 1 and 2, and nuclear magnetic data are shown as follows:
1 H NMR (CDCl 3 , 500 MHz) δ 12.27 (s, 1H), 8.95 (d, J = 8.6 Hz, 1H), 8.31 (d, J = 8.6 Hz, 1H), 8.17 - 8.13 (m, 3H), 7.90 (d, J = 8.0 Hz, 1H), 7.82 - 7.78 (m, 1H), 7.66 - 7.63 (m, 1H), 7.50 (t, J = 8.2 Hz, 2H), 7.31 (t, J = 7.4 Hz, 1H); 13 C NMR (CDCl 3 , 125 MHz) δ188.05, 150.42, 145.01, 138.82, 137.13, 130.43, 129.72, 129.10, 128.92, 128.13, 127.69, 126.57, 122.77, 121.11。
the structure of the target product is presumed to be as follows from the above data:
example 2
2-methylquinoline (0.2 mmol), 3-methylaniline (0.4 mmol), elemental sulfur (0.6 mmol) and solvent DMSO (2 mL) were sequentially added into a dry Schlenk reaction tube, after the sample was added, the sample was pumped in a vacuum pump, then nitrogen was injected for gas replacement, after three times of replacement, the reaction was stopped after 11 hours at 140 ℃, and the sample was cooled to room temperature. The reaction was checked by Thin Layer Chromatography (TLC) and, after the starting material had reacted, the reaction was terminated and the mixture in the reaction tube was cooled to room temperature. And (3) carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, rotating powder, and performing column chromatography separation and purification to obtain a target product with a yield of 75%.
The hydrogen spectrogram and the carbon spectrogram of the target product are respectively shown in fig. 3 and 4, and the nuclear magnetic data are shown as follows:
1 H NMR (CDCl 3 , 500 MHz) δ12.20 (s, 1H), 8.93 (d, J = 8.6 Hz, 1H), 8.27 (d, J = 8.6 Hz, 1H), 8.14 (d, J = 8.4 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H), 7.88 (t, J = 8.1 Hz, 2H), 7.78 (t, J = 7.4 Hz, 1H), 7.62 (t, J = 7.6 Hz,1H), 7.37 (t, J = 7.8 Hz ,1H), 7.12 (d, J = 7.5 Hz, 1H), 2.44 (s, 3H); 13 C NMR (CDCl 3 , 125 MHz) δ187.76, 150.37, 144.93, 138.81, 138.69, 137.01, 130.33, 129.65, 128.99, 128.67, 128.04, 127.62, 127.36, 123.19, 121.03, 119.81, 21.44。
the structure of the target product is presumed to be as follows from the above data:
example 3
2-methylquinoline (0.2 mmol), 4-methylaniline (0.4 mmol), elemental sulfur (0.6 mmol) and solvent DMSO (2 mL) were sequentially added into a dry Schlenk reaction tube, after the sample was added, the sample was pumped in a vacuum pump, then nitrogen was injected for gas replacement, after three times of replacement, the reaction was stopped after 11 hours at 140 ℃, and the sample was cooled to room temperature. The reaction was checked by Thin Layer Chromatography (TLC) and, after the starting material had reacted, the reaction was terminated and the mixture in the reaction tube was cooled to room temperature. And (3) carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, rotating powder, and performing column chromatography separation and purification to obtain a target product with a yield of 77%.
The hydrogen spectrogram and the carbon spectrogram of the target product are respectively shown in fig. 5 and 6, and the nuclear magnetic data are shown as follows:
1 H NMR (CDCl 3 , 500 MHz) δ12.16 (s, 1H), 8.92 (d, J = 8.5 Hz, 1H), 8.26 (d, J = 8.5 Hz 1H), 8.12 (d, J = 8.4 Hz, 1H), 7.98 (d, J = 8.1 Hz, 2H), 7.85 (d, J = 8.1 Hz, 1H), 7.76 (t, J = 7.9 Hz, 1H), 7.60 (t, J = 7.5 Hz, 1H), 7.27 (d, J = 8.0 Hz, 2H), 2.39 (s, 3H); 13 C NMR (CDCl 3 , 125 MHz) δ187.58, 150.38, 144.93, 136.97, 136.41, 136.27, 130.30, 129.62, 129.37, 128.96, 127.99, 127.59, 126.68, 121.03, 21.12。
the structure of the target product is presumed to be as follows from the above data:
example 4
2-methylquinoline (0.2 mmol), 2-methylbenzylamine (0.4 mmol), elemental sulfur (0.6 mmol) and solvent DMSO (2 mL) were sequentially added to a dry Schlenk reaction tube, after the sample was added, the sample was evacuated by an oil pump, then nitrogen was injected to perform gas displacement, after three times of displacement, the reaction was stopped after 11 hours at 140 ℃, and the sample was cooled to room temperature. The reaction was checked by Thin Layer Chromatography (TLC) and, after the starting material had reacted, the reaction was terminated and the mixture in the reaction tube was cooled to room temperature. And (3) carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, rotating powder, and performing column chromatography separation and purification to obtain a target product with the yield of 68%.
The hydrogen spectrogram and the carbon spectrogram of the target product are shown in fig. 7 and 8 respectively, and nuclear magnetic data are shown as follows:
1 H NMR (CDCl 3 , 500 MHz) δ 10.43 (s, 1H), 8.87 (d, J = 8.7 Hz, 1H), 8.27 (d, J = 8.7 Hz, 1H), 8.03 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 7.7 Hz, 1H), 7.73 - 7.70 (m, 1H), 7.60 - 7.57 (m, 1H), 7.39 (d, J = 7.2 Hz, 1H), 7.30 - 7.22 (m, 4H), 5.09 (d, J = 5.4 Hz, 2H), 2.40 (s, 3H); 13 C NMR (CDCl 3 , 125 MHz) δ 190.83, 150.04, 145.41, 136.97, 136.91, 134.38, 130.69, 130.20, 129.78, 129.15, 129.13, 128.20, 127.95, 127.61, 126.31, 121.37, 48.38, 19.23。
the structure of the target product is presumed to be as follows from the above data:
example 5
2-methylquinoline (0.2 mmol), 2-bromobenzylamine (0.4 mmol), elemental sulfur (0.6 mmol) and solvent DMSO (2 mL) were sequentially added into a dry Schlenk reaction tube, after the sample was added, the sample was pumped in a vacuum pump, then nitrogen was injected for gas replacement, after three times of replacement, the reaction was stopped after 11 hours at 140 ℃, and the reaction was cooled to room temperature. The reaction was checked by Thin Layer Chromatography (TLC) and, after the starting material had reacted, the reaction was terminated and the mixture in the reaction tube was cooled to room temperature. And (3) carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, rotating powder, and performing column chromatography separation and purification to obtain a target product with the yield of 70%.
The hydrogen spectrogram and the carbon spectrogram of the target product are shown in fig. 9 and 10 respectively, and nuclear magnetic data are shown as follows:
1 H NMR (CDCl 3 , 500 MHz) δ10.84(s, 1H), 8.92 (d, J = 8.6 Hz, 1H), 8.33 (d, J = 8.6 Hz, 1H), 8.15 (d, J = 8.5 Hz, 1H), 7.93 (d, J = 8.2 Hz, 1H), 7.81 (t, J = 8.3 Hz, 1H), 7.69 - 7.65 (m, 2H), 7.58 (d, J = 7.6 Hz, 1H), 7.37 (t, J = 7.6 Hz, 1H), 7.26 (t, J = 7.8 Hz, 1H), 5.31 (d, J = 6.0 Hz, 2H); 13 C NMR (CDCl 3 , 125 MHz) δ 191.39, 149.98, 145.37, 136.88, 135.63, 132.95, 130.54, 130.22, 129.84, 129.47, 129.14, 128.00, 127.63, 127.59, 123.99, 121.39, 49.60。
the structure of the target product is presumed to be as follows from the above data:
example 6
2-methylquinoline (0.2 mmol), 3-bromobenzylamine (0.4 mmol), elemental sulfur (0.6 mmol) and solvent DMSO (2 mL) were sequentially added into a dry Schlenk reaction tube, after the sample was added, the sample was pumped in a vacuum pump, then nitrogen was injected for gas replacement, after three times of replacement, the reaction was stopped after 11 hours at 140 ℃, and the reaction was cooled to room temperature. The reaction was checked by Thin Layer Chromatography (TLC) and, after the starting material had reacted, the reaction was terminated and the mixture in the reaction tube was cooled to room temperature. And (3) carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, rotating powder, and performing column chromatography separation and purification to obtain a target product, wherein the yield is 62%.
The hydrogen spectrogram and the carbon spectrogram of the target product are respectively shown in fig. 11 and 12, and the nuclear magnetic data are shown as follows:
1 H NMR (CDCl 3 , 500 MHz) δ 10.55 (s, 1H), 8.77 (d,J = 8.6 Hz, 1H), 8.20 (d, J = 8.7 Hz, 1H), 7.99 (d, J = 8.5 Hz, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.66 (t, J = 8.0 Hz, 1H), 7.54 - 7.49 (m, 2H), 7.38 (d, J= 8.0 Hz, 1H), 7.29 (d, J = 7.6 Hz, 1H), 7.17 (d, J = 7.5 Hz, 1H), 5.04 (d, J = 5.8 Hz, 2H); 13 C NMR (CDCl 3 , 125 MHz) δ 191.65, 149.91, 145.38, 138.81, 137.02, 131.08, 130.99, 130.38, 130.33, 129.77, 129.23, 128.09, 127.67, 126.73, 122.84, 121.47, 48.94。
the structure of the target product is presumed to be as follows from the above data:
example 7
2-methylquinoline (0.2 mmol), 4-methylbenzylamine (0.4 mmol), elemental sulfur (0.6 mmol) and solvent DMSO (2 mL) were sequentially added to a dry Schlenk reaction tube, after the sample was added, the sample was pumped in a vacuum pump, then nitrogen was injected to perform gas displacement, after three times of displacement, the reaction was stopped after 11 hours at 140 ℃, and the sample was cooled to room temperature. The reaction was checked by Thin Layer Chromatography (TLC) and, after the starting material had reacted, the reaction was terminated and the mixture in the reaction tube was cooled to room temperature. And (3) carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, rotating powder, and performing column chromatography separation and purification to obtain a target product with the yield of 65%.
The hydrogen spectrogram and the carbon spectrogram of the target product are shown in fig. 13 and 14 respectively, and the nuclear magnetic data are shown as follows:
1 H NMR (CDCl 3 , 500 MHz) δ10.59 (s, 1H), 8.92 (d, J = 8.6 Hz, 1H), 8.31 (d, J = 8.6 Hz, 1H), 8.08 (d, J = 8.5 Hz, 1H), 7.90 (d, J = 8.0 Hz, 1H), 7.78 - 7.75 (m, 1H), 7.65 - 7.62 (m, 1H), 7.39 (d, J = 8.0 Hz, 2H), 7.20 (d, J = 7.8 Hz, 2H), 5.12 (d, J = 5.6 Hz, 2H), 2.42 (s, 3H); 13 C NMR (CDCl 3 , 125 MHz) δ190.97, 150.10, 145.40, 137.69, 136.88, 133.40, 130.20, 129.77, 129.54, 129.14, 128.24, 127.95, 127.62, 121.44, 49.77, 21.14。
the structure of the target product is presumed to be as follows from the above data:
example 8
2-methylquinoline (0.2 mmol), 2, 4-dimethoxybenzylamine (0.4 mmol), elemental sulfur (0.6 mmol) and solvent DMSO (2 mL) were sequentially added into a dry Schlenk reaction tube, after the sample was added, the sample was pumped in a vacuum pump, then nitrogen was injected for gas replacement, after three times of replacement, the reaction was stopped after 11 hours at 140 ℃, and the sample was cooled to room temperature. The reaction was checked by Thin Layer Chromatography (TLC) and, after the starting material had reacted, the reaction was terminated and the mixture in the reaction tube was cooled to room temperature. And (3) carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, rotating powder, and performing column chromatography separation and purification to obtain a target product with the yield of 39%.
The hydrogen spectrogram and the carbon spectrogram of the target product are shown in fig. 15 and fig. 16 respectively, and the nuclear magnetic data are shown as follows:
1 H NMR (CDCl 3 , 500 MHz) δ10.68 (s, 1H), 8.87 (d, J = 8.6 Hz, 1H), 8.26 (d, J = 8.6 Hz, 1H), 8.40 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 8.0 Hz, 1H), 7.75 - 7.72(m, 1H), 7.61 - 7.58 (m, 1H), 7.35 (d, J = 8.2 Hz, 1H), 6.53 (d, J = 5.0 Hz, 1H), 6.49 - 6.47 (m, 1H), 5.05 (d, J = 5.6 Hz, 2H), 3.92 (s, 3H), 3.82 (s, 3H); 13 C NMR (CDCl 3 , 125 MHz) δ190.12, 160.91, 158.91, 150.48, 145.46, 136.73, 131.11, 130.08, 129.82, 129.08, 127.82, 127.63, 121.52, 116.95, 104.09, 98.78, 55.48, 55.42, 45.44。
the structure of the target product is presumed to be as follows from the above data:
example 9
2-methylquinoline (0.2 mmol), 3,4, 6-trimethylbenzylamine (0.4 mmol), elemental sulfur (0.6 mmol) and solvent DMSO (2 mL) were sequentially added into a dry Schlenk reaction tube, after the sample was added, the sample was pumped in a vacuum pump, then nitrogen was injected to perform gas displacement, after three times of displacement, the reaction was stopped after 11 hours at 140 ℃, and the sample was cooled to room temperature. The reaction was checked by Thin Layer Chromatography (TLC) and, after the starting material had reacted, the reaction was terminated and the mixture in the reaction tube was cooled to room temperature. And (3) carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, rotating powder, and performing column chromatography separation and purification to obtain a target product with the yield of 83%.
The hydrogen spectrogram and the carbon spectrogram of the target product are shown in fig. 17 and 18, respectively, and the nuclear magnetic data are shown as follows:
1 H NMR (CDCl 3 , 500 MHz) δ10.13 (s, 1H), 8.91 (d, J = 8.6 Hz, 1H), 8.27 (d, J = 8.6 Hz, 1H), 8.02 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 7.6 Hz, 1H), 7.70 - 7.68 (m, 1H), 7.60 - 7.57 (m, 1H), 6.94 (s, 2H), 5.04 (d, J = 4.7 Hz, 2H), 2.41 (s, 6H), 2.34 (s, 3H); 13 C NMR (CDCl 3 , 125 MHz) δ190.5, 151.01, 149.93, 145.36, 137.81, 136.73, 130.04, 129.69, 129.66, 129.14, 129.01, 127.81, 127,50, 121.16, 45.05, 20.90, 19.76。
the structure of the target product is presumed to be as follows from the above data:
example 10
2-methylquinoline (0.2 mmol), 2-pyridine methylamine (0.4 mmol), elemental sulfur (0.6 mmol) and solvent DMSO (2 mL) are sequentially added into a dry Schlenk reaction tube, after the sample is added, the sample is vacuumized by an oil pump, then nitrogen is injected for gas replacement, after three times of replacement, the reaction is stopped after 11 hours at 140 ℃, and the reaction is cooled to room temperature. The reaction was checked by Thin Layer Chromatography (TLC) and, after the starting material had reacted, the reaction was terminated and the mixture in the reaction tube was cooled to room temperature. And (3) carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, rotating powder, and performing column chromatography separation and purification to obtain a target product with the yield of 66%.
The hydrogen spectrum and the carbon spectrum of the target product are shown in fig. 19 and 20, respectively, and the nuclear magnetic data are shown as follows:
1 H NMR (CDCl 3 , 500 MHz) δ10.68 (s, 1H), 8.83 (d, J = 8.6 Hz, 1H), 8.71 (s, 1H), 8.57 (t, J = 1 Hz, 1H), 8.27 (d, J = 8.6 Hz, 1H), 8.04 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 8.2 Hz, 1H), 7.79 (d, J = 7.8 Hz, 1H), 7.75 - 7.72(m, 1H), 7.60 (t, J = 7.8 Hz, 1H), 7.31 - 7.26 (m, 1H), 5.16 (d, J = 6.0 Hz, 2H); 13 C NMR (CDCl 3 , 125 MHz) δ191.89, 149.82, 149.48, 149.20, 145.34, 137.03, 135.88, 132.32, 130.35, 129.70, 129.20, 128.10, 127.65, 123.65, 121.37, 46.90。
the structure of the target product is presumed to be as follows from the above data:
example 11
2-methylquinoline (0.2 mmol), 1-naphthylmethylamine (0.4 mmol), elemental sulfur (0.6 mmol) and solvent DMSO (2 mL) are sequentially added into a dry Schlenk reaction tube, after the sample is added, the sample is vacuumized by an oil pump, then nitrogen is injected for gas replacement, after three times of replacement, the reaction is stopped after 11 hours at 140 ℃, and the reaction is cooled to room temperature. The reaction was checked by Thin Layer Chromatography (TLC) and, after the starting material had reacted, the reaction was terminated and the mixture in the reaction tube was cooled to room temperature. And (3) carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, rotating powder, and performing column chromatography separation and purification to obtain the target yield with 65 percent.
The hydrogen spectrogram and the carbon spectrogram of the target product are shown in fig. 21 and 22 respectively, and the nuclear magnetic data are shown as follows:
1 H NMR (CDCl 3 , 500 MHz) δ 10.57 (s, 1H), 8.91 (d, J = 8.6 Hz, 1H), 8.25 (d, J = 8.6 Hz, 1H), 8.08 (t, J = 7.4 Hz, 1H), 7.91 (d, J = 8.8 Hz, 2H), 7.88 (d, J = 8.4 Hz, 1H), 7.82 (d, J = 8.1 Hz, 1H), 7.66 - 7.61 (m, 2H), 7.57 - 7.53 (m, 3H), 7.49 (t, J = 7.8 Hz, 1H), 5.54 (d, J = 5.4 Hz, 2H); 13 C NMR (CDCl 3 , 125 MHz) δ 190.71, 149.94, 145.30, 136.85, 133.82, 131.91, 131.66, 130.10, 129.69, 129.06, 129.00, 128.75, 127.90, 127.51, 127.34, 126.83, 126.09, 125.38, 123.51, 121.36, 48.30。
the structure of the target product is presumed to be as follows from the above data:
Claims (2)
1. a method for synthesizing quinoline-2-thiocarboxamide compounds under the conditions of no catalyst and no additive is characterized by comprising the following steps:
will have the formula 2-methylquinoline, < > as shown in the formula>
Or->
Adding a sulfur source and a solvent into a reaction tube, stirring for reaction at 130-140 ℃, cooling to room temperature after the reaction is finished, and separating and purifying a product to obtain a quinoline-2-thiocarboxamide compound shown in the formula;
the solvent is dimethyl sulfoxide;
the sulfur source is elemental sulfur;
the said
Selected from: aniline, 2-chloroaniline, 3-methylaniline, 4-methylaniline, benzidine;
the said
Selected from: benzylamine, 4- (trifluoromethyl) benzylamine, 4-fluorobenzylamine, 4-chlorobenzylamine, 4-methylbenzylamine, 3-bromobenzylamine, 3- (trifluoromethyl) benzylamine, 2-methylbenzylamine, 2-chlorobenzylamine, 2-bromobenzylamine, 3, 5-bis (trifluoromethyl) benzylamine, 2, 4-dimethylbenzylamine, 2,4, 6-trimethylbenzylamine, 2-pyridinemethylamine, 1-naphthylmethylamine;
the said
Or->
The molar ratio of the addition amount of the (E) and the 2-methylquinoline is 1.2-3:1; the molar ratio of the addition amount of the sulfur source to the 2-methylquinoline is 2-4:1; the reaction temperature is 130-140 ℃; the reaction time is 9-15 hours.
2. The synthetic method of claim 1 wherein the separation and purification is performed by: extracting the reaction liquid with ethyl acetate, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, evaporating the organic solvent under reduced pressure to obtain a crude product, and purifying by column chromatography to obtain the quinoline-2-thiocarboxamide compound.
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Application publication date: 20200925 Assignee: Hunan Hengfei Biopharmaceutical Co.,Ltd. Assignor: Hengyang Normal University Contract record no.: X2023980047818 Denomination of invention: A synthesis method of quinoline-2-thioformamide compounds without catalysts and additives Granted publication date: 20230609 License type: Common License Record date: 20231123 |