CN111635363A - Method for synthesizing N, N' -disubstituted benzimidazole onium derivative and metal organic salt thereof by mechanochemical method - Google Patents
Method for synthesizing N, N' -disubstituted benzimidazole onium derivative and metal organic salt thereof by mechanochemical method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 48
- -1 N, N' -disubstituted benzimidazole Chemical class 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 19
- 239000002184 metal Substances 0.000 title claims abstract description 19
- 150000003839 salts Chemical class 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 21
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 16
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- WGVYCXYGPNNUQA-UHFFFAOYSA-N 1-(bromomethyl)-2-methylbenzene Chemical compound CC1=CC=CC=C1CBr WGVYCXYGPNNUQA-UHFFFAOYSA-N 0.000 claims description 3
- NVNPLEPBDPJYRZ-UHFFFAOYSA-N 1-(bromomethyl)-4-fluorobenzene Chemical compound FC1=CC=C(CBr)C=C1 NVNPLEPBDPJYRZ-UHFFFAOYSA-N 0.000 claims description 3
- WZRKSPFYXUXINF-UHFFFAOYSA-N 1-(bromomethyl)-4-methylbenzene Chemical compound CC1=CC=C(CBr)C=C1 WZRKSPFYXUXINF-UHFFFAOYSA-N 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 3
- UVECLJDRPFNRRQ-UHFFFAOYSA-N ethyl trifluoromethanesulfonate Chemical compound CCOS(=O)(=O)C(F)(F)F UVECLJDRPFNRRQ-UHFFFAOYSA-N 0.000 claims description 3
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 238000003701 mechanical milling Methods 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 4
- 101150003085 Pdcl gene Proteins 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 30
- 239000007787 solid Substances 0.000 description 25
- 239000000843 powder Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 229910000831 Steel Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 229940058303 antinematodal benzimidazole derivative Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003863 physical function Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention relates to a method for synthesizing N, N' -disubstituted benzimidazole onium derivatives and metal organic salts thereof by a mechanochemical method. First with benzimidazole, alkyl or aryl substituents and K2CO3The raw materials are ground for 2 hours in a planetary ball mill at the room temperature under the condition of no solvent and the frequency of 37.5Hz to obtain the target product. The N, N' -disubstituted benzimidazole onium derivative and the metal chloride PdCl are quickly prepared by a mechanical grinding method2The metal organic salt of (1). The method provided by the invention is simple to operate, short in reaction time, environment-friendly, high in purity of the prepared product and high in yield.
Description
Technical Field
The invention belongs to the field of chemical synthesis, relates to a method for synthesizing N, N '-disubstituted benzimidazole onium and metal organic salt thereof, and particularly relates to a method for synthesizing N, N' -disubstituted benzimidazole onium and metal organic salt thereof by a mechanochemical method under the condition of normal temperature and no solvent.
Background
N, N' -disubstituted benzimidazole onium is used as a micromolecular catalyst and applied to various organic reactions. At the same time, it is also an important class of ligands for linking to modern organometallic chemistry. Firstly, N, N' -disubstituted benzimidazole onium as a ligand can form a complex with transition metal, and is widely applied to catalysis, biology and materials science; in addition, the metal organic salt formed by the action of N, N' -disubstituted benzimidazole onium ligand and metal ion through hydrogen bond is also an effective catalyst, and is used as a novel ionic liquid to be applied to the research of electrochemical sensors. At present, most of the synthesis methods of N, N' -disubstituted benzimidazole onium and metal organic salts thereof stay in the traditional solution synthesis method, and the reaction is balanced by means of heat energy generated by long-time heating reflux. Some compounds require more severe reaction conditions for preparation, such as high temperature and high pressure, special catalysts, and the like. Therefore, the problems of complicated solvent use, complicated purification and separation process, long reaction time, low yield and the like are common problems in the preparation of compounds by a solution method.
Mechanochemistry is a solid-state synthesis method, is a green synthesis method carried out by mechanical force without the assistance of a solvent or a trace amount of solvent, and provides a method for synthesizing a new compound and also provides more selective paths for researching the chemical properties and physical functions of the compound under special conditions. Mechanochemistry has numerous advantages over traditional solution reactions: (1) the reaction conditions are mild, and the energy consumption and the cost are saved to a certain extent; (2) the problems of natural environment pollution and harm to human health caused by the solvent are fundamentally solved because no solvent is involved in the reaction process; (3) the reaction rate and the conversion rate can be improved; (4) some reactions that cannot be carried out in solution can be achieved.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for synthesizing N, N' -disubstituted benzimidazole onium and metal organic salt thereof by a mechanochemical method under the condition of normal temperature and no solvent.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for synthesizing N, N' -disubstituted benzimidazole onium derivatives by a mechanochemical method comprises the following steps: with benzimidazole, alkyl or aryl substituents and K2CO3Grinding the raw material in a planetary ball mill at room temperature without solvent to obtain a crude product of the N, N' -disubstituted benzimidazole onium derivative.
Further, in the above process, the alkyl or aryl substituent is selected from the group consisting of 4-fluorobenzyl bromide, 1-benzyl bromide, 4-methylbenzyl bromide, 2-methylbenzyl bromide, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate and allyl bromide.
Further, the above process, in a molar ratio, benzimidazole, alkyl or aryl substituent, K2CO3＝1:3:1.5。
Further, the above method, in a planetary ball mill, is carried out for 2 to 3 hours at a frequency of 37.5 Hz.
Further, the method comprises the following post-processing steps: suspending the obtained crude N, N' -disubstituted benzimidazole onium derivative product in dichloromethane, filtering, and evaporating the filtrate under reduced pressure; washing the obtained residue with tetrahydrofuran to obtain the N, N' -disubstituted benzimidazole onium derivative.
A method for synthesizing metal organic salt of N, N' -disubstituted benzimidazole onium derivative by mechanochemical method includes the following steps: and (3) rapidly grinding the N, N '-disubstituted benzimidazole onium derivative and the metal chloride by using a mechanical grinding method to prepare the corresponding metal organic salt of the N, N' -disubstituted benzimidazole onium derivative.
Further, the above method, the mechanical grinding method, is grinding in agate mortar and pestle for 3-5 minutes.
Further, in the above method, the metal chloride is PdCl2。
Further, the above method, N' -disubstituted benzimidazole derivatives, metal chloride, is 2:1 in a molar ratio.
The invention has the beneficial effects that:
1. the preparation method of the N, N' -disubstituted benzimidazole onium derivative and the metal organic salt thereof provided by the invention has the characteristics of simple operation, environmental protection, short reaction time, environmental friendliness, high product purity, high yield and the like.
2. The method provided by the invention does not need high-temperature and high-pressure conditions, does not need solvents, metal catalysts and the like, can be used for preparing the N, N' -disubstituted benzimidazole onium, and has the advantages of green and mild reaction conditions, and convenient and fast experiment.
Drawings
FIG. 1 shows the crystal structure of a metal organic salt of N, N' -disubstituted benzimidazole derivative L2 prepared in example 8 with palladium chloride.
FIG. 2 is a graph comparing the powders of the ground product and the recrystallized product of the metal organic salt formed from N, N' -disubstituted benzimidazole onium derivative L2 and palladium chloride prepared in example 8.
Detailed Description
In order that the invention may be better understood, the invention will now be further described by way of example.
Example 1
Benzimidazole (0.59g, 5.0mmol), 4-fluorobenzyl bromide (15.0mmol) and anhydrous K2CO3(7.5mmol) was added to a 100mL steel grinding jar with 8 stainless steel balls (diameter 9 mm). The jar was closed and milled in a planetary ball mill (pbm) at a frequency of 37.5Hz for 2 hours to give a white solid.
The white solid obtained from the reaction was worked up: suspending the obtained white solid in about 20mL of dichloromethane, filtering to remove KBr generated in the system, and evaporating under reduced pressure; the residue was then washed 2-3 times with tetrahydrofuran to give a white powder, the desired N, N' -disubstituted benzimidazolium derivative, designated as L1.
Taking small amount of powder, respectively1H NMR、13C NMR measurement.
1H NMR(300MHz,DMSO)(ppm)9.97(d,J＝5.2Hz,1H),8.00–7.95(m,2H),7.67–7.59(m,6H),7.32–7.25(m,4H),5.77(s,4H).
13C NMR(100MHz,DMSO)162.3(ppm)(d,J＝245.3Hz),142.7,131.1,131.0(d,J＝8.5Hz),130.1(d,J＝3.1Hz),126.9,115.9(d,J＝21.7Hz),114.1,49.4.
Example 2
Benzimidazole (0.59g, 5.0mmol), 1-benzyl bromide (15.0mmol) and anhydrous K2CO3(7.5mmol) was added to a 100mL steel grinding jar with 8 stainless steel balls (diameter 9 mm). The jar was closed and milled in a planetary ball mill (pbm) at a frequency of 37.5Hz for 2 hours to give a white solid.
The white solid obtained from the reaction was worked up: suspending the obtained white solid in about 20mL of dichloromethane, filtering to remove KBr generated in the system, and evaporating under reduced pressure; the residue was then washed 2-3 times with tetrahydrofuran to give a white powder, the desired N, N' -disubstituted benzimidazolium derivative, designated as L2.
Taking small amount of powder, respectively1H NMR、13C NMR measurement.
1H NMR(500MHz,DMSO)(ppm)10.23(s,1H),8.02–7.97(m,2H),7.65–7.61(m,2H),7.57–7.55(m,4H),7.45–7.37(m,6H),5.84(s,4H).
13C NMR(125MHz,DMSO)(ppm)142.7,134.0,131.1,129.1,128.9,128.4,126.9,114.1,50.1.
Example 3
Benzimidazole (0.59g, 5.0mmol), 4-methylbenzyl bromide (15.0mmol) and anhydrous K2CO3(7.5mmol) was added to a 100mL steel grinding jar with 8 stainless steel balls (diameter 9 mm). The jar was closed and milled in a planetary ball mill (pbm) at a frequency of 37.5Hz for 2 hours to give a white solid.
The white solid obtained from the reaction was worked up: suspending the obtained white solid in about 20mL of dichloromethane, filtering to remove KBr generated in the system, and evaporating under reduced pressure; the residue was then washed 2-3 times with tetrahydrofuran to give a white powder, the desired N, N' -disubstituted benzimidazolium derivative, designated as L3.
Taking small amount of powder, respectively1H NMR、13C NMR measurement.
1H NMR(400MHz,DMSO)(ppm)10.10(s,1H),7.99–7.93(m,2H),7.64–7.59(m,2H),7.44–7.42(m,4H),7.23–7.21(m,4H),5.74(s,4H),2.28(s,6H).
13C NMR(125MHz,DMSO)(ppm)142.5,138.4,131.1,131.0,129.7,128.5,126.9,114.2,50.0,20.8.
Example 4
Benzimidazole (0.59g, 5.0mmol), 2-methylbenzyl bromide (15.0mmol) and anhydrous K2CO3(7.5mmol) was added to a 100mL steel grinding jar with 8 stainless steel balls (diameter 9 mm). Closing the grinding cylinder and in a planetary ball mill (pbm) at a frequency of 37.5HzTrituration was carried out for 2 hours to give a white solid.
The white solid obtained from the reaction was worked up: suspending the obtained white solid in about 20mL of dichloromethane, filtering to remove KBr generated in the system, and evaporating under reduced pressure; the residue was then washed 2-3 times with tetrahydrofuran to give a white powder, the desired N, N' -disubstituted benzimidazolium derivative, designated as L4.
Taking small amount of powder, respectively1H NMR、13C NMR measurement.
1H NMR(500MHz,DMSO)(ppm)9.73(s,1H),7.95–7.90(m,2H),7.68–7.64(m,2H),7.31–7.30(m,4H),7.23–7.19(m,2H),7.13–7.11(m,2H),5.83(s,4H),2.34(s,6H).
13C NMR(125MHz,DMSO)(ppm)143.0,136.6,132.0,131.6,131.0,128.9,128.2,127.1,126.6,114.2,48.7,18.9.
Example 5
Benzimidazole (0.59g, 5.0mmol), methyl triflate (15.0mmol) and anhydrous K2CO3(7.5mmol) was added to a 100mL steel grinding jar with 8 stainless steel balls (diameter 9 mm). The jar was closed and milled in a planetary ball mill (pbm) at a frequency of 37.5Hz for 2 hours to give a white solid.
The white solid obtained from the reaction was worked up: washing the obtained white solid with diethyl ether, suspending the white solid in 20mL of dichloromethane, filtering, and evaporating the obtained solid under reduced pressure; the residue was then washed 2-3 times with tetrahydrofuran to give a white powder, the desired N, N' -disubstituted benzimidazolium derivative, designated as L5.
Taking small amount of powder, respectively1H NMR、13C NMR measurement.
1H NMR(400MHz,CD3CN)(ppm)9.02(s,1H),7.87–7.82(m,2H),7.72–7.67(m,2H),4.05–4.05(m,6H).
13C NMR(100MHz,CD3CN)(ppm)143.2,133.1,127.9,122.1(q,J＝320.8Hz),114.2,34.2.
Example 6
Benzimidazole (0.59g, 5.0 mm)ol), ethyl trifluoromethanesulfonate (15.0mmol) and anhydrous K2CO3(7.5mmol) was added to a 100mL steel grinding jar with 8 stainless steel balls (diameter 9 mm). The jar was closed and milled in a planetary ball mill (pbm) at a frequency of 37.5Hz for 2 hours to give a white solid.
The white solid obtained from the reaction was worked up: washing the obtained white solid with diethyl ether, suspending the white solid in 20mL of dichloromethane, filtering, and evaporating the obtained solid under reduced pressure; the residue was then washed 2-3 times with tetrahydrofuran to give a white powder, the desired N, N' -disubstituted benzimidazolium derivative, designated as L6.
Taking small amount of powder, respectively1H NMR、13C NMR measurement.
1H NMR(400MHz,CD3CN)(ppm)9.09(s,1H),7.91–7.87(m,2H),7.71–7.66(m,2H),4.48(q,J＝7.3Hz,4H),1.59(t,J＝7.3Hz,6H).
13C NMR(100MHz,CD3CN)(ppm)141.4,132.5,127.9,122.1(q,J＝320.7Hz),114.4,43.6,14.6.
Example 7
Benzimidazole (0.59g, 5.0mmol), allyl bromide (15.0mmol) and K2CO3(7.5mmol) was added to a 100mL steel grinding jar with 8 stainless steel balls (diameter 9 mm). The jar was closed and milled in a planetary ball mill (pbm) at a frequency of 37.5Hz for 2 hours to give a pale yellow solid.
The light yellow solid obtained from the reaction was worked up: suspending the obtained light yellow solid in about 20mL of dichloromethane, filtering to remove KBr generated in the system, and evaporating under reduced pressure; the residue was then washed 2-3 times with tetrahydrofuran to give a pale yellow powder as the desired N, N' -disubstituted benzimidazolium derivative, designated as L7.
Taking small amount of powder, respectively1H NMR、13C NMR measurement.
1H NMR(400MHz,DMSO)(ppm)9.95(s,1H),8.05–8.00(m,2H),7.70–7.65(m,2H),6.18–6.08(m,2H),5.48–5.37(m,4H),5.24–5.23(m,4H).
13C NMR(100MHz,DMSO)(ppm)142.5,131.1,131.0,126.7,120.6,114.0,48.9.
The synthesis conditions and yields of the seven N, N' -disubstituted benzimidazole derivatives obtained in examples 1 to 7 were compared with those reported in the literature. The results are shown in Table 1.
TABLE 1 mechanical Synthesis of N, N' -disubstituted benzimidazolium derivatives L1-L7 in comparison with the relevant literature reports
As can be seen from Table 1, the imidazolium salt ligands, which have been synthesized in the literature by the conventional solution reflux method, can be obtained by a planetary ball mill (pbm) under solvent-free conditions (L2, L4 and L7): the synthesis of L2 by the conventional reflux method requires 8 hours of reaction in acetonitrile solvent, the yield is 76%, but the L2 can be obtained by mechanical ball milling method in solvent-free condition for 2 hours, and the yield is 67.9%; the L4 is synthesized by a conventional reflux method and needs two steps, the reaction time is as long as 50 hours, but the L4 can be obtained by a one-step method under the condition of no solvent by using a mechanical ball milling method and can be obtained by grinding for 2 hours with the yield of 51.4%; in addition, the synthesis of L7 by the conventional reflux method required a reaction in ethanol solvent for 24 hours to obtain a yield of 65%, but by mechanical ball milling in the absence of solvent for 2 hours, it could be obtained in a yield of 78.1%. More importantly, there are no compounds reported in literature, and the compounds can also be synthesized by mechanical synthesis directly using a planetary ball mill, such as ligands L1, L3, L5 and L6, and the target compounds can be synthesized with yields of 71.9%, 71.1%, 80.2% and 84% respectively by mechanical ball milling for 2 hours in the absence of solvent.
Example 8
0.0758g N, N' -disubstituted benzimidazole onium derivative L2 and 0.0177g PdCl2Placing in an agate mortar, adding 1 drop of concentrated hydrochloric acidAnd 2-3 drops of methanol are ground for about 3 minutes, the powder in the mortar is changed from white and brownish red into orange, and when the powder is dry powder, the grinding is stopped, and a ground product is obtained.
And (3) recrystallization: transferring the obtained ground product into a conical flask, adding 3mL of methanol and 4mL of acetonitrile, and standing for 7-8 days to obtain a recrystallized product, namely an orange blocky crystal, namely the metal palladium organic salt of the N, N' -disubstituted benzimidazole onium derivative L2.
The prepared metal palladium organic salt of the N, N' -disubstituted benzimidazole onium derivative L2 is subjected to single crystal X-ray diffraction, and the result is shown in figure 1, and the three-dimensional structure of the product can be intuitively obtained from figure 1.
The obtained ground product and the obtained recrystallized product were subjected to X-ray powder diffraction experiments, respectively, and the results are shown in fig. 2, from which fig. 2, it can be seen that the powder diffraction peak of the recrystallized product and the powder diffraction peak of the ground product completely correspond to each other.
Claims (9)
1. A method for synthesizing N, N' -disubstituted benzimidazole onium derivatives by a mechanochemical method is characterized by comprising the following steps: with benzimidazole, alkyl or aryl substituents and K2CO3Grinding the raw material in a planetary ball mill at room temperature without solvent to obtain a crude product of the N, N' -disubstituted benzimidazole onium derivative.
2. The method of claim 1, wherein the alkyl or aryl substituent is selected from the group consisting of 4-fluorobenzyl bromide, 1-benzyl bromide, 4-methylbenzyl bromide, 2-methylbenzyl bromide, methyl triflate, ethyl triflate, and allyl bromide.
3. The process according to claim 1, wherein the molar ratio of benzimidazole to alkyl or aryl substituent to K2CO3＝1:3:1.5。
4. A method according to claim 1, characterized in that milling is carried out in a planetary ball mill at a frequency of 37.5Hz for 2-3 hours.
5. The method according to any one of claims 1 to 4, comprising a post-processing step of: suspending the obtained crude N, N' -disubstituted benzimidazole onium derivative product in dichloromethane, filtering, and evaporating the filtrate under reduced pressure; washing the obtained residue with tetrahydrofuran to obtain the N, N' -disubstituted benzimidazole onium derivative.
6. A method for synthesizing metal organic salt of N, N' -disubstituted benzimidazole onium derivative by mechanochemical method is characterized by comprising the following steps: and (3) rapidly grinding the N, N '-disubstituted benzimidazole onium derivative and the metal chloride by using a mechanical grinding method to prepare the corresponding metal organic salt of the N, N' -disubstituted benzimidazole onium derivative.
7. The method of claim 6, wherein the mechanical milling is in an agate mortar and pestle for 3-5 minutes.
8. The method according to claim 6 or 7, wherein the metal chloride is PdCl2。
9. The process according to claim 6 or 7, wherein the molar ratio of N, N' -disubstituted benzimidazole onium derivative to metal chloride is 2: 1.
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| CN113620919A (en) * | 2021-06-18 | 2021-11-09 | 浙江工业大学 | Mechanical ball-milling auxiliary synthesis method of 2-amino-3-cyano-4H-pyran compounds |
| CN118005605A (en) * | 2024-01-31 | 2024-05-10 | 扬州大学 | Method for synthesizing arylthianthrene onium salt under mechanochemical condition |
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Cited By (4)
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| CN113620919B (en) * | 2021-06-18 | 2023-12-12 | 浙江工业大学 | Mechanical ball milling assisted synthesis method of 2-amino-3-cyano-4H-pyran compound |
| CN118005605A (en) * | 2024-01-31 | 2024-05-10 | 扬州大学 | Method for synthesizing arylthianthrene onium salt under mechanochemical condition |
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