CN111704575A - Method for synthesizing quinoline-2-thiocarbamide compound under conditions of no catalyst and no additive - Google Patents
Method for synthesizing quinoline-2-thiocarbamide compound under conditions of no catalyst and no additive Download PDFInfo
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- CN111704575A CN111704575A CN202010653476.0A CN202010653476A CN111704575A CN 111704575 A CN111704575 A CN 111704575A CN 202010653476 A CN202010653476 A CN 202010653476A CN 111704575 A CN111704575 A CN 111704575A
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- benzylamine
- methylquinoline
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- -1 quinoline-2-thiocarbamide compound Chemical class 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- 239000000654 additive Substances 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 title claims abstract description 12
- 230000000996 additive effect Effects 0.000 title claims abstract description 11
- 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 23
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 7
- 238000001308 synthesis method Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 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
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 238000004440 column chromatography Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003786 synthesis reaction Methods 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
- 230000015572 biosynthetic process Effects 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
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- HDDAGABOUKEMAG-UHFFFAOYSA-N quinoline-2-carbothioamide Chemical class C1=CC=CC2=NC(C(=S)N)=CC=C21 HDDAGABOUKEMAG-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
- 150000001875 compounds Chemical class 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
- WGTASENVNYJZBK-UHFFFAOYSA-N 3,4,5-trimethoxyamphetamine Chemical compound COC1=CC(CC(C)N)=CC(OC)=C1OC WGTASENVNYJZBK-UHFFFAOYSA-N 0.000 claims description 2
- LYUQWQRTDLVQGA-UHFFFAOYSA-N 3-phenylpropylamine Chemical compound NCCCC1=CC=CC=C1 LYUQWQRTDLVQGA-UHFFFAOYSA-N 0.000 claims description 2
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-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
- DBGROTRFYBSUTR-UHFFFAOYSA-N [4-(trifluoromethoxy)phenyl]methanamine Chemical compound NCC1=CC=C(OC(F)(F)F)C=C1 DBGROTRFYBSUTR-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
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 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
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000011403 purification operation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 42
- 238000001228 spectrum Methods 0.000 description 42
- 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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 238000011221 initial treatment Methods 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 239000000203 mixture 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
- 238000000746 purification Methods 0.000 description 11
- 238000009987 spinning Methods 0.000 description 11
- 239000007858 starting material Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 150000003556 thioamides Chemical class 0.000 description 3
- 150000001408 amides Chemical class 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
- 238000012271 agricultural production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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 method for synthesizing a quinoline-2-thiocarbamide compound under the conditions of no catalyst and no additive. The synthesis method comprises the following steps: adding 2-methylquinoline, aromatic amine or aliphatic amine compounds, a sulfur source and a solvent into a reaction tube, stirring and reacting at 130-150 ℃, cooling to room temperature after the reaction is finished, and separating and purifying a product to obtain the quinoline-2-thiocarboxamide compound. The invention provides a method for synthesizing a catalyst-free and additive-free quinoline-2-thiocarbamide compound. The reaction condition is simple, the 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-thiocarbamide compound.
Description
Technical Field
The invention belongs to the field of quinoline-2-thiocarboxamide compounds, and particularly relates to a method for synthesizing a quinoline-2-thiocarboxamide compound under the conditions of no catalyst and no additive.
Background
Amide compounds are widely applied in the field of pesticides, but the development and application of the amide compounds are limited due to poor water solubility of the amide compounds. With the continuous progress of research, the thioamide compounds can replace known amide pesticides (Wangbuyun, Zhangda Yong, Wudaming, pesticide 2010, 49 and 170.), so that the agricultural production is more environment-friendly. Besides playing a role in the field of medicines, thioamide compounds are also frequently used as synthons in organic synthesis for synthesizing various sulfur-containing or nitrogen-containing heterocyclic organic compounds due to excellent reactivity. The process for the synthesis of thioamides generally uses amides or amines as substrates, requires metal catalysts or additives, increases the emission of waste and causes problems with product metal residues (a BCharette, 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 the compound by using a reagent which is low in toxicity, convenient, safe and easily available and developing the compound simply, conveniently, greenly and efficiently.
The invention provides a method for synthesizing a quinoline-2-thiocarbamide compound by taking 2-methylquinoline, aromatic amine or aliphatic amine as a substrate without a catalyst or an additive. The reaction condition is simple, the 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-thiocarbamide compound.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provides a method for synthesizing quinoline-2-thiocarbamide 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-thiocarbamide compound.
The purpose of the invention is realized by the following technical scheme.
A method for synthesizing quinoline-2-thiocarboxamide compounds in the absence of a catalyst and an additive comprises the following steps: adding 2-methylquinoline, aromatic amine or aliphatic amine, a sulfur source and a solvent into a reaction tube, stirring and reacting at 130-150 ℃, cooling 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:
in the formula, R1One selected from hydrogen, methyl and halogen radical; r2Is 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: 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.
Furthermore, the molar ratio of the added aromatic amine or aliphatic amine compound to 2-methylquinoline is 1.2-3: 1, and 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, and preferably 3: 1.
Further, the solvent is dimethyl sulfoxide.
Further, the stirring temperature is 130-150 ℃, and preferably 140 ℃.
Further, the stirring reaction time is 9-15 hours, preferably 11 hours.
Further, the separation and purification operations are as follows: and extracting the reaction liquid by using ethyl acetate, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, decompressing, steaming and removing the organic solvent to obtain a crude product, and purifying by using column chromatography to obtain the quinoline-2-thiocarbamide compound.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides a method for synthesizing a quinoline-2-thiocarbamide compound under the conditions of no catalyst and no additive. From the perspective of green chemistry, under the condition of no metal catalyst and no additive, the invention synthesizes the quinoline-2-thiocarbamide compound by taking easily obtained 2-methylquinoline, aromatic amine or aliphatic amine compound as a substrate and elemental sulfur as a sulfur source. The reaction condition is simple, the 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-thiocarbamide compound.
Drawings
Fig. 1 and 2 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 1, respectively.
Fig. 3 and 4 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 2, respectively.
Fig. 5 and 6 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 3, respectively.
Fig. 7 and 8 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 4, respectively.
Fig. 9 and 10 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 5, respectively.
Fig. 11 and 12 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 6, respectively.
Fig. 13 and 14 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 7, respectively.
Fig. 15 and 16 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 8, respectively.
Fig. 17 and 18 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 9, respectively.
Fig. 19 and 20 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 10, respectively.
Fig. 21 and 22 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 11, respectively.
Detailed description of the invention
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, but the scope and implementation of the present invention are not limited thereto.
Example 1
2-methylquinoline (0.2mmol), aniline (0.4mmol), elemental sulfur (0.6mmol) and a solvent DMSO (2mL) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, nitrogen is injected for gas replacement, after three times of replacement, the reaction is stopped after 11 hours at 140 ℃, and the cooling is carried out to the room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, spinning powder, and performing column chromatography separation and purification to obtain a target product with a yield of 80%.
The hydrogen spectrogram and the carbon spectrogram of the target product are respectively shown in fig. 1 and fig. 2, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)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= 7.4Hz, 1H);13C NMR (CDCl3, 125 MHz)188.05, 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 through the data:
example 2
2-methylquinoline (0.2mmol), 3-methylaniline (0.4mmol), elemental sulfur (0.6mmol) and a solvent DMSO (2mL) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, 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 monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (3) extracting, collecting an organic layer, spinning powder, and performing column chromatography separation and purification to obtain a target product with the yield of 75%.
The hydrogen spectrum and the carbon spectrum of the target product are respectively shown in fig. 3 and 4, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)12.20 (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);13C NMR (CDCl3,125 MHz)187.76, 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 through the data:
example 3
2-methylquinoline (0.2mmol), 4-methylaniline (0.4mmol), elemental sulfur (0.6mmol) and a solvent DMSO (2mL) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, 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 monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, spinning powder, and performing column chromatography separation and purification to obtain a target product with a yield of 77%.
The hydrogen spectrum and the carbon spectrum of the target product are respectively shown in fig. 5 and 6, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)12.16 (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);13C NMR (CDCl3, 125 MHz)187.58, 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 through the data:
example 4
2-methylquinoline (0.2mmol), 2-methylbenzylamine (0.4mmol), elemental sulfur (0.6mmol) and a solvent DMSO (2mL) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, 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 monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, spinning powder, and performing column chromatography separation and purification to obtain a target product with a yield of 68%.
The hydrogen spectrum and the carbon spectrum of the target product are respectively shown in fig. 7 and fig. 8, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)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);13C NMR (CDCl3, 125 MHz)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 through the data:
example 5
2-methylquinoline (0.2mmol), 2-bromobenzylamine (0.4mmol), elemental sulfur (0.6mmol) and a solvent DMSO (2mL) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, nitrogen is injected for gas replacement, after the replacement is carried out for three times, the reaction is stopped after 11 hours at 140 ℃, and the cooling is carried out to the room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, spinning powder, and performing column chromatography separation and purification to obtain a target product with the yield of 70%.
The hydrogen spectrum and the carbon spectrum of the target product are respectively shown in fig. 9 and fig. 10, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)10.84(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);13C NMR(CDCl3, 125 MHz)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 through the data:
example 6
2-methylquinoline (0.2mmol), 3-bromobenzylamine (0.4mmol), elemental sulfur (0.6mmol) and a solvent DMSO (2mL) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, nitrogen is injected for gas replacement, after the replacement is carried out for three times, the reaction is stopped after 11 hours at 140 ℃, and the cooling is carried out to the room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (3) extracting, collecting an organic layer, spinning powder, and performing column chromatography separation and purification to obtain a target product with the yield of 62%.
The hydrogen spectrum and the carbon spectrum of the target product are respectively shown in fig. 11 and 12, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)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);13C NMR(CDCl3, 125 MHz)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 through the data:
example 7
2-methylquinoline (0.2mmol), 4-methylbenzylamine (0.4mmol), elemental sulfur (0.6mmol) and a solvent DMSO (2mL) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, 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 monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, spinning powder, and performing column chromatography separation and purification to obtain a target product with the yield of 65%.
The hydrogen spectrum and the carbon spectrum of the target product are respectively shown in fig. 13 and fig. 14, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)10.59 (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);13C NMR (CDCl3, 125 MHz)190.97, 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 through the data:
example 8
2-methylquinoline (0.2mmol), 2, 4-dimethoxybenzylamine (0.4mmol), elemental sulfur (0.6mmol) and a solvent DMSO (2mL) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, nitrogen is injected for gas replacement, after the replacement is carried out for three times, the reaction is stopped after 11 hours at 140 ℃, and the cooling is carried out to the room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, spinning powder, and performing column chromatography separation and purification to obtain a target product with the yield of 39%.
The hydrogen spectrum and the carbon spectrum of the target product are respectively shown in fig. 15 and 16, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)10.68 (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);13C NMR (CDCl3, 125 MHz)190.12, 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 through the data:
example 9
2-methylquinoline (0.2mmol), 3,4, 6-trimethylbenzylamine (0.4mmol), elemental sulfur (0.6mmol) and a solvent DMSO (2mL) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, nitrogen is injected for gas replacement, after three times of replacement, the reaction is stopped after 11 hours at 140 ℃, and the cooling is carried out to the room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, spinning powder, and performing column chromatography separation and purification to obtain a target product with the yield of 83%.
The hydrogen spectrum and the carbon spectrum of the target product are respectively shown in fig. 17 and fig. 18, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)10.13 (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);13C NMR (CDCl3, 125 MHz)190.5, 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 through the data:
example 10
2-methylquinoline (0.2mmol), 2-pyridylmethylamine (0.4mmol), elemental sulfur (0.6mmol) and a solvent DMSO (2mL) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, 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 monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: extracting, collecting an organic layer, spinning 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 respectively shown in fig. 19 and fig. 20, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)10.68 (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= 8.5Hz, 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);13C NMR (CDCl3, 125 MHz)191.89, 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 through the data:
example 11
2-methylquinoline (0.2mmol), 1-naphthylmethylamine (0.4mmol), elemental sulfur (0.6mmol) and a solvent DMSO (2mL) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, 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 monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (3) extracting, collecting an organic layer, spinning powder, and performing column chromatography separation and purification to obtain the target productivity with the yield of 65%.
The hydrogen spectrum and the carbon spectrum of the target product are respectively shown in fig. 21 and 22, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)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);13C NMR(CDCl3, 125 MHz)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 through the data:
Claims (8)
1. a method for synthesizing quinoline-2-thiocarboxamide compounds without a catalyst and an additive is characterized by comprising the following steps: adding 2-methylquinoline, aromatic amine or aliphatic amine, a sulfur source and a solvent into a reaction tube, stirring and reacting at 130-150 ℃, cooling to room temperature after the reaction is finished, and separating and purifying a product to obtain the quinoline-2-thiocarboxamide compound.
2. The method of claim 1, wherein the chemical reaction equation of the synthesis process is as follows:
in the formula, R1One selected from hydrogen, methyl and halogen radical; r2Is selected from alkyl.
3. The synthesis process according to claim 1 or 2, characterized in that the aromatic amine compound is selected from: aniline, 2-chloroaniline, 3-methylaniline, 4-methylaniline, benzidine.
4. The synthesis process according to claim 1 or 2, characterized in that the fatty amine-based compound is chosen from: 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.
5. The synthesis method according to claims 1 to 4, wherein the molar ratio of the added aromatic amine or aliphatic amine compound to 2-methylquinoline is 1.2-3: 1.
6. The method of synthesis according to claims 1-4, characterized in that the sulfur source is elemental sulfur; the molar ratio of the added sulfur source to 2-methylquinoline is 2-4: 1.
7. The synthetic method of claims 1-4 wherein the solvent is dimethyl sulfoxide; the reaction temperature is 130-150 ℃; the reaction time is 9-15 hours.
8. The synthesis method according to claims 1 to 4, characterized in that the separation and purification operations are: and extracting the reaction liquid by using ethyl acetate, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, decompressing, steaming and removing the organic solvent to obtain a crude product, and purifying by using column chromatography to obtain the quinoline-2-thiocarbamide compound.
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| CN112500324A (en) * | 2020-12-12 | 2021-03-16 | 浙江大学衢州研究院 | Method for preparing thioamide 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 |
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