CN108689943A - Super molecular compound containing ruthenium and its preparation method and application - Google Patents
Super molecular compound containing ruthenium and its preparation method and application Download PDFInfo
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Abstract
Super molecular compound containing ruthenium and its preparation method and application is related to a kind of novel super molecular compound containing ruthenium and its preparation method and application and a kind of novel benzimidazole ligand and preparation method thereof.The benzimidazole ligand toxicity of the present invention is low, is a kind of novel benzimidazole ligand, and toxicity is far below pyridine.The super molecular compound containing ruthenium of the present invention, is a kind of novel super molecular compound containing ruthenium, has good inhibition to human lung cancer cell line HCT-116 and A549.
Description
Technical field
The present embodiment belongs to organic chemical synthesis field, and in particular to super molecular compound containing ruthenium and preparation method thereof and answers
With.
Background technology
Full tumour refers to body under the effect of various tumorigenesis factors, the cell paraplasm of local organization and formed swollen
Block.Tumour can be divided into benign tumour and malignant tumour, and malignant tumour (also referred to as cancer) can destroy tissue, the structure of organ and work(
Can, cause hemorrhagic necrosis and the infection of tissue or organ, patient may finally be dead due to organ failure.Ruthenium base
Closing object has good active anticancer, wherein important one kind is to drive arene ruthenium (II) supermolecule of structure certainly by coordinate bond
Assemble anticancer compound.
Suss-Fink has synthesized first arene ruthenium (II) supermolecule complex in 1997.Arene ruthenium (II) receives
Body is a kind of ruthenium polymerization of olefin using catalyst compound of partial encapsulation, its structure is to pass through bridge similar to piano stool (also referred to as molecular-clips)
Two ruthenium (II) ions for joining ligand connection, remain that there are one complexible coordination sites on each metal ion.By arene ruthenium (II)
Acceptor and different angle either different types of ligand obtained with self assembly means two dimension or three-dimensional structure multinuclear it is super
Molecular self-assembling compound.In the prior art it is most of about anticancer p-cymene ruthenium self assemblies compound mostly be use double end pyrrole
Pyridine class or carboxylic acids ligand.
Invention content
The purpose of the present invention is to provide containing novel ruthenium super molecular compound, preparation method and its application.
It is another object of the present invention to provide a kind of novel benzimidazole ligands.
For achieving the above object, technical scheme is as follows:
Benzimidazole ligand with structure shown in Formulas I:
Wherein R is n-C4H9O or n-C8H17O。
The present invention also provides the preparation methods of benzimidazole ligand described in above-mentioned technical proposal, include the following steps:
(1) dust technology and fuming nitric aicd are added drop-wise in the acetic acid solution of 1,2- dialkoxy benzenes and nitration reaction occurs, obtained
To nitration product, 1, the 2- dialkoxy benzenes are 1,2- Dibutoxy Benzenes or 1, bis- octyloxy benzene of 2-;
(2) nitration product, Pd/C catalyst, absolute ethyl alcohol and the hydrazine hydrate mixing obtained the step (1) occurs
Reduction reaction obtains reduzate;
(3) reduzate that the step (2) obtains is mixed into generation cyclization with formic acid and reacts into imidazole ring, obtain benzo
Imdazole derivatives, the benzimidizole derivatives are 5,6- dibutoxy benzo imidazoles or 5, bis- octyloxy benzimidazoles of 6-;
(4) benzimidizole derivatives that obtain the step (3), to bromobenzene, potassium carbonate, copper oxide and N, N- dimethyl
Ullmann reaction occurs for formamide mixing, obtains the benzimidazole ligand with structure shown in Formulas I.
The present invention also provides super molecular compounds containing ruthenium, have structure shown in Formula II:
Wherein, A is the compound with structure shown in formula A1, A2 or A3:
L is the compound with structure shown in formula L1, L2, L4 or Formulas I:
Wherein R is n-C4H9O or n-C8H17O。
The present invention also provides super molecular compounds containing ruthenium, have structure shown in formula III:
Wherein A is the compound with structure shown in formula A1, A2 or A3:
L is the compound with structure shown in formula L3:
The present embodiment additionally provides the preparation method of the super molecular compound containing ruthenium described in above-mentioned technical proposal, including following
Step:A compounds, L compounds and polar organic solvent are mixed, coordination driving self-assembling reaction occurs, obtains supermolecule containing ruthenium
Compound.
Preferably, the time of the coordination driving self-assembling reaction is 24~48h.
Preferably, further include after the coordination driving self-assembling reaction:Coordination is driven into the pole in self-assembling reaction product
Property organic solvent remove after be added ether carry out centrifugal treating.
Preferably, the rotating speed of the centrifugal treating is 2900rpm, and the time of the centrifugal treating is 10min.
Preferably, the polar organic solvent includes dichloromethane and/or methanol.
The present embodiment additionally provides the super molecular compound containing ruthenium described in above-mentioned technical proposal in preparing anticancer drug
Using.
Compared with prior art, beneficial effects of the present invention:The benzimidazole ligand toxicity of the present invention is low, is a kind of novel
Benzimidazole ligand, toxicity be far below pyridine.The super molecular compound containing ruthenium of the present invention is a kind of novel containing ruthenium
Super molecular compound has good inhibition to human lung cancer cell line HCT-116 and A549.
Description of the drawings
Fig. 1 is L5 made from the embodiment of the present invention 131H-NMR spectrum;
Fig. 2 is L5 made from the embodiment of the present invention 1313C-NMR spectrograms;
Fig. 3 is L6 made from the embodiment of the present invention 161H-NMR spectrum;
Fig. 4 is L6 made from the embodiment of the present invention 1613C-NMR spectrograms.
Specific implementation mode:
The present invention provides the benzimidazole ligands with structure shown in Formulas I:
Wherein R is n-C4H9O or n-C8H17O。
In the present invention, the structure of the benzimidazole ligand with structure shown in Formulas I is as follows:
The present invention also provides the preparation methods of benzimidazole ligand described in above-mentioned technical proposal, include the following steps:
(1) dust technology and fuming nitric aicd are added drop-wise in the acetic acid solution of 1,2- dialkoxy benzenes and nitration reaction occurs, obtained
To nitration product, 1, the 2- dialkoxy benzenes are 1,2- Dibutoxy Benzenes or 1, bis- octyloxy benzene of 2-;
(2) nitration product, Pd/C catalyst, absolute ethyl alcohol and the hydrazine hydrate mixing obtained the step (1) occurs
Reduction reaction obtains reduzate;
(3) reduzate that the step (2) obtains is mixed into generation cyclization with formic acid and reacts into imidazole ring, obtain benzo
Imdazole derivatives, the benzimidizole derivatives are 5,6- dibutoxy benzo imidazoles or 5, bis- octyloxy benzimidazoles of 6-;
(4) benzimidizole derivatives that obtain the step (3), to bromobenzene, potassium carbonate, copper oxide and N, N- dimethyl
Ullmann reaction occurs for formamide mixing, obtains the benzimidazole ligand with structure shown in Formulas I.
Dust technology and fuming nitric aicd are added drop-wise in the acetic acid solution of 1,2- dialkoxy benzenes by the present invention occurs nitration reaction,
Nitration product is obtained, 1, the 2- dialkoxy benzenes are 1,2- Dibutoxy Benzenes or 1, bis- octyloxy benzene of 2-.In the present invention, institute
It is added dropwise again after stating the preferably mixing of nitric acid and fuming nitric aicd.In the present invention, it is described be added dropwise it is preferable to use constant pressure funnel into
Row.In the present invention, the dropwise addition carries out preferably in ice bath, and the temperature of the ice bath is preferably 0 DEG C.
In the present invention, the amount ratio of the dust technology, fuming nitric aicd, 1,2- dialkoxy benzenes and acetic acid is preferably
3.5mL:30mL:18.0mol:40mL.
In the present invention, the temperature of the nitration reaction is preferably room temperature, does not need additional heating or cooling, the nitre
The time for changing reaction is preferably 3~5h, and the time of more preferably 4h, the nitration reaction are reached with reaction system after completion of dropwise addition
Start to calculate when room temperature.In the present invention, it is preferred to which ice bath is removed in completion of dropwise addition recession, reaction system is made to reach the temperature of nitration reaction
Degree.
The present invention does not have special restriction to the source of 1, the 2- dialkoxy benzenes, using known to those skilled in the art
Preparation method be made, specifically, such as mixing catechol with n,N-Dimethylformamide, be slowly added to Carbon Dioxide
Brominated alkanes are added after potassium, nucleophilic substitution 18h occur at 90 DEG C, extracted with water/ethyl acetate, merge organic phase,
Then the washing of NaOH aqueous solutions uses saturated common salt water washing three times three times, anhydrous sodium sulfate drying, Rotary Evaporators are spin-dried for molten
Agent obtains 1,2- dialkoxy benzenes.In the present invention, the brominated alkanes are bromination of n-butane or n-octane bromide.
In the present invention, the volume ratio of water and ethyl acetate is preferably 1 in the water/ethyl acetate:0.2~1:0.5.
After the completion of nitration reaction, the present invention preferably mixes the reaction solution that nitration reaction obtains with mixture of ice and water successively,
It filters, wash, absolute ethyl alcohol reflux, it is cooling to be precipitated, filter to obtain nitration product again.The present invention is to the mixture of ice and water, water
And the dosage of absolute ethyl alcohol, suction filtration, alcohol reflux, the cooling concrete operations for being precipitated and filtering again do not have special restriction, use
Means well known to those skilled in the art.
In the present invention, the nitration product has structure shown in following formula:
Wherein R is n-C4H9O- or n-C8H17O-。
After obtaining nitration product, the present invention mixes the nitration product, Pd/C catalyst, absolute ethyl alcohol and hydrazine hydrate
Reduction reaction occurs, obtains reduzate.In the present invention, the nitration product, Pd/C catalyst, absolute ethyl alcohol and hydrazine hydrate
Amount ratio be preferably 12.8mol:90mg:40mL:6.3mL.
In the present invention, the temperature of the reduction reaction is preferably 80 DEG C, and the time of the reduction reaction is preferably 12h.
The present invention does not have the source of the catalyst special restriction, is using Pd/C catalyst well known to those skilled in the art
It can.
In the present invention, further preferably include vacuum and exchange nitrogen before the reduction reaction carries out.In the present invention, the pumping
The number of vacuum air-changing is preferably 3 times.In the present invention, the pressure of the nitrogen is preferably normal pressure.
After the completion of reduction reaction, the reaction solution that reduction reaction obtains preferably is cooled to room temperature, crosses diatom by the present invention successively
Soil and be spin-dried for solvent, obtain reduzate.In the present invention, described to be cooled to room temperature preferably natural cooling.In the present invention,
The diatomite of crossing is to remove the solid kind by-product generated in reduction reaction such as Pd/C catalyst.In the present invention, institute
It states and is spin-dried for solvent and is carried out preferably in Rotary Evaporators.
In the present invention, the structure of the reduzate is shown in following formula:
After obtaining reduzate, the reduzate is mixed generation cyclization with formic acid and reacts into imidazole ring by the present invention, is obtained
To benzimidizole derivatives, the benzimidizole derivatives are 5,6- dibutoxy benzo imidazoles or 5, bis- octyloxy benzo miaows of 6-
Azoles.In the present invention, the amount ratio of the reduzate and formic acid is preferably 12.8mol:50mL.
In the present invention, further preferably include vacuum and exchange nitrogen before the cyclization reaction is carried out at imidazole ring.In the present invention
In, the number for vacuumizing ventilation is preferably 3 times.In the present invention, the pressure of the nitrogen is preferably normal pressure.
In the present invention, the cyclization reaction is preferably 12h at the time of imidazole ring.
It reacts into after the completion of imidazole ring reacts, the present invention further preferably removes reaction solution that reaction is obtained at imidazole ring successively
Formic acid, adjusting pH value are neutrality, ethyl acetate extraction, washing, saturated common salt water washing, are spin-dried for solvent, ether washing and filtering,
Obtain benzimidizole derivatives.In the present invention, the mode except formic acid removal is preferably evaporated under reduced pressure.In the present invention, institute
It is preferably ammonium hydroxide or saturated sodium carbonate solution to state and adjust the reagent that pH value uses.The present invention eats the ethyl acetate, water, saturation
The dosage of brine and ether does not have special restriction, using mode well known to those skilled in the art.
After obtaining benzimidizole derivatives, the present invention by the benzimidizole derivatives, to bromobenzene, potassium carbonate, copper oxide
It is mixed with n,N-Dimethylformamide and ullmann reaction occurs, obtain the benzimidazole ligand with structure shown in Formulas I.In this hair
In bright, the benzimidizole derivatives are preferably to the amount ratio of bromobenzene, potassium carbonate, copper oxide and n,N-Dimethylformamide
122.4mmol:50.4mmol:124.8mmol:6.0mmol:60mL.
In the present invention, the temperature of the ullmann reaction is preferably 150 DEG C, and the reagent of the ullmann reaction is preferably
48h。
In the present invention, further preferably include vacuumizing displacement nitrogen before the ullmann reaction carries out.In the present invention, institute
It is preferably 3 times to state and vacuumize the number of displacement nitrogen.In the present invention, the pressure of the nitrogen is preferably normal pressure.
After the completion of ullmann reaction, the present invention further preferably includes crossing diatomite, two successively to the reaction solution of ullmann reaction
Chloromethanes washing, the drying of saturated common salt water washing, anhydrous sodium sulfate, is spin-dried for solvent, pentane washing, filtering and column chromatography at washing,
Obtain the benzimidazole ligand with structure shown in Formulas I.The present invention to the diatomite, dichloromethane, water, saturated salt solution,
The dosage of anhydrous sodium sulfate and pentane does not have special restriction, using mode well known to those skilled in the art.In this hair
In bright, the eluant, eluent that the column chromatography uses is ethyl acetate.
The present invention also provides the super molecular compounds containing ruthenium with structure shown in Formula II:
Wherein, A is the compound with structure shown in formula A1, A2 or A3:
L is the compound with structure shown in formula L1, L2, L4 or Formulas I:
Wherein R is n-C4H9O- or n-C8H17O-。
The present invention also provides the super molecular compounds containing ruthenium with structure shown in formula III:
Wherein A is the compound with structure shown in formula A1, A2 or A3:
L is the compound with structure shown in formula L3:
In the present invention, the A is connected with L by coordinate bond, cationic portion be A and L-shaped at rectangle or
Person's triangular prism, anion part are trifluoromethanesulfonic acid root.
The present invention also provides the preparation methods of the super molecular compound containing ruthenium described in above-mentioned technical proposal, including following step
Suddenly:A compounds, L compounds and polar organic solvent are mixed, coordination driving self-assembling reaction occurs, obtains supermolecular containing ruthenium
Close object.
In the present invention, when the L is with the compound of structure shown in formula L1, L2, L4 or Formulas I, the A and L's
Molar ratio is 1:1, when the L is with the compound of structure shown in formula L3, the molar ratio of the A and L are 3:2.
The present invention does not have the source of the A special restriction, using preparation method system well known to those skilled in the art
, specifically, such as:
The preparation method of A1:Bis- (the 4- isopropyl methyls phenyl) rutheniums (II) of dichloro and oxamide are dissolved in methanol/chloroform (V:
V=1:1) in the mixed solvent vacuumizes displacement nitrogen, and reaction is flowed back, waits for that reaction system is cooled to room temperature, uses rotary evaporation
Solvent is spin-dried for by instrument, and residue is dissolved in dichloromethane, and filters.Filtrate is spin-dried for, faint yellow solid is obtained.The solid that will be obtained again
It is dissolved in methanol with silver trifluoromethanesulfonate equivalent, stirs 2~4h at room temperature, white AgCl precipitations are precipitated, then use diatomite
Filtering, methanol wash three times, obtain filtrate and are threaded to slightly dry, are precipitated yellow solid after ether is added, centrifuge (2500r/min)
10min discards supernatant liquor, obtains target product and is then dried in vacuo.
The preparation method of A2:By bis- (the 4- isopropyl methyls phenyl) rutheniums (II) of dichloro, 2,5- dihydroxy -1,4- benzoquinones and second
Sour sodium is placed in eggplant type bottle, adds 25mL ethyl alcohol, vacuumizes displacement nitrogen, is flowed back with vigorous stirring for 24 hours.Wait for reaction system
When being cooled to room temperature, (2500r/min) 10min is centrifuged, supernatant is discarded, obtains dark red solid, use ethyl alcohol, acetone, second
Ether respectively washes twice.Solid and silver trifluoromethanesulfonate are dissolved in methanol, stir 2~4h at room temperature, white AgCl precipitations are precipitated, so
It is filtered afterwards using diatomite, obtains filtrate and be threaded to slightly dry, addition ether, precipitation dark red solid.It centrifuges (2500r/min)
10min obtains target product and is then dried in vacuo.
The preparation method of A3:Take bis- (the 4- isopropyl methyls phenyl) rutheniums (II) of dichloro, Nai Qian and sodium acetate that pears type bottle is added
In, ethyl alcohol is added, is vigorously stirred lower reflux for 24 hours.It waits for that reaction system is cooled to room temperature, centrifuges (2500r/min) 10min, discard
Supernatant, solid use ethyl alcohol, acetone, ether to wash twice respectively, obtain brown solid.Solid is molten with silver trifluoromethanesulfonate
In methanol, stir 2~4h at room temperature, white AgCl be precipitated and precipitates, is then filtered using diatomite, obtain filtrate be threaded to it is slightly dry,
Ether is added, green solid is precipitated.(2500r/min) 10min is centrifuged, target product is obtained and is then dried in vacuo.
The present invention does not have the source of described L1, L2, L3 and L4 special restriction, use well known to those skilled in the art
Commercial goods are made using preparation method well known to those skilled in the art, specifically, such as:
The preparation method of L1:Isosorbide-5-Nitrae-mixes bromobenzene and imidazoles and potassium carbonate n,N-Dimethylformamide, replaces nitrogen
Gas three times, reacts 48h under the conditions of 150 DEG C.Crude product crosses diatomite, and dichloromethane washing merges organic phase, water is then added
It washes three times, three times, anhydrous sodium sulfate drying, solvent is spin-dried for obtaining solid and be washed with pentane saturated common salt water washing with Rotary Evaporators
It washs, yellow solid is obtained by filtration using cloth funnel, crude product carries out column chromatography (EA) and obtain white solid to be target product.
The preparation method of L2:Bromobenzene, imidazoles, potassium carbonate and n,N-Dimethylformamide between 1,3- are mixed, nitrogen is replaced
Three times, 48h is reacted under the conditions of 150 DEG C.Crude product crosses diatomite, and dichloromethane washing merges organic phase, washing is then added
Three times, three times, anhydrous sodium sulfate drying, solvent is spin-dried for obtaining solid and be washed with pentane saturated common salt water washing with Rotary Evaporators
It washs, yellow solid is obtained by filtration using cloth funnel, crude product carries out column chromatography (EA) and obtain white solid to be target product.
The preparation method of L3:Tribromo-benzene, imidazoles, potassium carbonate and n,N-Dimethylformamide mix by between, replace nitrogen three
It is secondary, react 48h under the conditions of 150 DEG C.Crude product crosses diatomite, and dichloromethane washing merges organic phase, washing three is then added
Secondary, three times, anhydrous sodium sulfate drying, solvent is spin-dried for obtaining solid and be washed with pentane saturated common salt water washing with Rotary Evaporators,
Yellow solid is obtained by filtration using cloth funnel, crude product carries out column chromatography (EA) and obtain white solid to be target product.
The preparation method of L4:Bromobenzene, benzimidazole, potassium carbonate and DMSO between 1,3- are mixed, replace nitrogen three times,
48h is reacted under the conditions of 150 DEG C.Crude product crosses diatomite, then dichloromethane washing is extracted with methylene chloride/water, merged organic
Phase, anhydrous sodium sulfate drying are spin-dried for wash with pentane after solvent that yellow solid is obtained by filtration, and crude product carries out column chromatography (EA) must
To white solid.
In the present invention, the time of the coordination driving self-assembling reaction is preferably 24~48h, and the coordination drives from group
The temperature of reaction cartridge is preferably room temperature, does not need additional heating or cooling.
In the present invention, further preferably include after the coordination driving self-assembling reaction:By coordination driving self-assembling reaction production
Polar organic solvent in object is added ether after removing and carries out centrifugal treating.The present invention is to the side for removing polar organic solvent
Formula does not have special restriction, using mode known to people in the art, specifically, as purged.The present invention is to ether
Dosage does not have special restriction, and super molecular compound containing ruthenium is enabled to be precipitated.
In the present invention, the rotating speed of the centrifugal treating is preferably 2900rpm, and the time of the centrifugal treating is preferably
10min.After obtaining centrifugation product, the present invention preferably further includes also being capable of ether washing centrifugation product.Use of the present invention to ether
Amount and centrifugation number do not have special restriction, using mode well known to those skilled in the art.
In the present invention, the polar organic solvent preferably includes CD3One kind or several in OD, DCM and methanol (MeOH)
Kind, mixture, the CD of more preferably DCM and methanol3The mixture of OD and DCM.In the present invention, the DCM and methanol is mixed
It is preferably 1 to close the volume ratio of DCM and methanol in object:1, the CD3CD in the mixture of OD and DCM3The volume ratio of OD and DCM is excellent
It is selected as 1:1.
The present invention also provides the answering in preparing anticancer drug of the super molecular compound containing ruthenium described in above-mentioned technical proposal
With.
In the present invention, various pharmaceutical dosage forms can be made (comprising tablet, capsule, spray in the super molecular compound containing ruthenium
Mist, effervescent tablet, ointment, injection) it uses.
In the present invention, the cancer cell preferably includes HCT-116 (human colon cancer cell) or A549 (human lung carcinoma cell).
In the present invention, the effective dose of the super molecular compound containing ruthenium is preferably 0.37 μm~50 μm.
With reference to embodiment to super molecular compound containing ruthenium provided by the invention and its preparation method and application, benzo miaow
Azoles ligand and preparation method thereof is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The preparation of A1:Take bis- (the 4- isopropyl methyls phenyl) rutheniums (II) (306.2mg, 0.5mmol) of dichloro and oxamide
(62.1mg, 0.5mmol) is placed in 100mL eggplant type bottles, is dissolved in 30mL methanol/chloroform (V:V=1:1) in the mixed solvent is taken out true
Reaction reflux 6h is waited for that reaction system is cooled to room temperature, is spin-dried for solvent using Rotary Evaporators, residue is molten by empty substitution nitrogen
In dichloromethane, and filter.Filtrate is spin-dried for, faint yellow solid is obtained.Obtained solid and silver trifluoromethanesulfonate etc. are worked as again
Amount is dissolved in methanol, stirs 2h at room temperature, and white AgCl is precipitated and precipitates, is then filtered using diatomite, obtain filtrate be threaded to it is slightly dry,
Yellow solid is precipitated after ether is added.(2500r/min) 10min is centrifuged, supernatant liquor is discarded, obtains target product then vacuum
It is dry.
The preparation of L1:Isosorbide-5-Nitrae-is weighed to bromobenzene 24.6g (105mmol), 17.5g (205mmol) imidazoles and 36.0g
100mL n,N-Dimethylformamide is added in 200mL eggplant-shape bottles in (260mmol) potassium carbonate, nitrogen is replaced three times, at 150 DEG C
Under the conditions of react 48h.Crude product crosses diatomite, and dichloromethane washing merges organic phase, washing then is added three times, saturation food
Three times, anhydrous sodium sulfate drying, solvent is spin-dried for obtaining solid and be washed with pentane, leaked using cloth salt water washing with Rotary Evaporators
Yellow solid is obtained by filtration in bucket, and crude product carries out column chromatography (solvent:Ethyl acetate) to obtain white solid be target product.
Accurate weighing ligand L 1 (2.1mg, 0.01mmol) is catalyzed with metal acceptor A1 (8.6mg, 0.01mmol) in 8mL
It in bottle, is dissolved using methanol, coordination driving self assembly occurs for stirring at room temperature for 24 hours, and solvent, which is blown to 0.2mL, is added ether analysis
Go out solid, centrifuges 10min using centrifuge (2900r/min), discard supernatant liquor, then washed once with ether, obtain metal
Rectangle super molecular compound containing ruthenium R1.
Metal rectangular super molecular compound containing ruthenium R1 is characterized:
1H NMR(400MHz,CD3OD+DMSO-d6V/V=5/1) 8.57 (s, 4H, H of δ2-imidazole),7.94(s,4H,
H5-imidazole),7.71(s,8H,Ph),6.85(s,4H,H4-imidazole), 6.21 (d, J=6.4Hz, 8H, Php-cymene),6.03
(d, J=6.4Hz, 8H, Php-cymene),3.10–3.00(m,4H,CH),2.46(s,12H,CH3), 1.57 (d, J=6.9Hz,
24H,CH(CH3)2);
13C NMR(100MHz,CD3OD+DMSO-d6V/V=5/1):δ172.3,139.0,135.8,130.7,130.1,
127.4,123.5,122.6,121.0,120.4,102.2,99.2,83.9,81.7,32.3,22.8,18.5;
MS(ESI):m/z calcd for[R1-2OTf]2+:918.05;found:917.96;elemental
analysis:Calcd (%) for C72H76N8O20F12S4Ru4:C 40.52,H 3.59,N 5.25;found:C 40.55,H
3.57,N 5.49。
Embodiment 2
The preparation of A2:Take bis- (the 4- isopropyl methyls phenyl) rutheniums (II) (138.7mg, 0.30mmol) of dichloro, 2,5- dihydroxies
Base-Isosorbide-5-Nitrae-benzoquinones (42.0mg, 0.30mmol) and sodium acetate (29.5mg, 0.36mmol) are placed in 100mL eggplant type bottles, are added
25mL ethyl alcohol, vacuumizes displacement nitrogen, flows back with vigorous stirring for 24 hours.When reaction system is cooled to room temperature, centrifugation
(2500r/min) 10min, discards supernatant, obtains dark red solid, using ethyl alcohol, acetone, ether respectively washes twice.It will consolidate
Body is dissolved in methanol with silver trifluoromethanesulfonate, stirs 4h at room temperature, and white AgCl precipitations are precipitated, is then filtered, is obtained using diatomite
Slightly dry, addition ether, precipitation dark red solid are threaded to filtrate.(2500r/min) 10min is centrifuged, obtains target product then
Vacuum drying.
Preparing for L1 is in the same manner as in Example 1.
Accurate weighing ligand L 1 (2.1mg, 0.01mmol) is catalyzed with metal acceptor A2 (9.1mg, 0.01mmol) in 8mL
It in bottle, is dissolved, is stirred at room temperature for 24 hours using methanol, solvent, which is blown to 0.2mL, is added ether, uses centrifuge (2500r/
Min 10min) is centrifuged, supernatant liquor is discarded, then washed once with ether, obtains metal rectangular super molecular compound containing ruthenium R2.
Structural characterization is carried out to metal rectangular super molecular compound containing ruthenium R2:
1H NMR(400MHz,CD3OD)δ8.46(s,4H,H2-imidazole),7.68(s,4H,H5-imidazole),7.62(s,
8H,Ph),6.76(s,4H,H4-imidazole), 6.04 (d, J=6.2Hz, 8H, Php-cymene), 5.83 (d, J=6.2Hz, 8H,
Php-cymene),5.79(s,4H,Hdobq),2.95–2.78(m,4H,CH),2.23(s,12H,CH3), 1.35 (d, J=6.9Hz,
24H,CH(CH3)2);
13C NMR(100MHz,CD3OD)δ185.4,139.9,136.8,131.0,123.7,121.2,104.1,102.6,
100.3,85.0,82.3,32.6,22.6,18.4;
MS(ESI):m/z calcd for[R2-2OTf]2+:968.57;found:968.95;elemental
analysis:Calcd (%) for C80H80N8O20F12S4Ru4:C 43.01,H 3.61,N 5.02;found:C 42.77,H
3.60,N 5.14。
Embodiment 3
The preparation method of A3:Take bis- (the 4- isopropyl methyls phenyl) rutheniums (II) (145.0mg, 0.24mmol) of dichloro, Nai Qian
(45.6mg, 0.23mmol) and sodium acetate (38.4mg, 0.47mmol) are added in 100mL pears type bottles, 25mL ethyl alcohol are added, acutely
The lower reflux of stirring is for 24 hours.It waits for that reaction system is cooled to room temperature, centrifuges (2500r/min) 10min, discard supernatant, solid uses second
Alcohol, acetone, ether wash twice respectively, obtain brown solid.Solid and silver trifluoromethanesulfonate are dissolved in methanol, stirred at room temperature
3h is precipitated white AgCl precipitations, is then filtered using diatomite, is obtained filtrate and is threaded to slightly dry, addition ether, is precipitated green solid
Body.(2500r/min) 10min is centrifuged, target product is obtained and is then dried in vacuo.
Preparing for L1 is in the same manner as in Example 1.
It weighs ligand L 1 (2.1mg, 0.01mmol) and is catalyzed bottle in 8mL with metal acceptor A3 (9.6mg, 0.01mmol)
In, dissolved using methanol, stir at room temperature for 24 hours, by solvent be blown to 0.2mL be added ether, using centrifuge (2500r/min) from
Heart 10min discards supernatant liquor, then washed once with ether, obtains metal rectangular super molecular compound containing ruthenium R3.
Structural characterization is carried out to metal rectangular super molecular compound containing ruthenium R3:
1H NMR(400MHz,CD3OD)δ8.39(s,4H,CH2-imidazole),7.58(s,8H,Ph),7.56(s,4H,
H5-imidazole),7.16(s,8H,Hdonq),6.97(s,4H,H4-imidazole), 5.82 (d, J=6.0Hz, 8H, Php-cymene),
5.60 (d, J=6.1Hz, 8H, Php-cymene),2.85–2.74(m,4H,CH),2.11(s,12H,CH3), 1.30 (d, J=
6.9Hz,24H,CH(CH3)2);
13C NMR(100MHz,CD3OD)δ172.3,138.6,138.4,136.8,130.7,123.6,121.1,112.7,
104.1,101.3,86.0,82.9,32.0,22.5,17.6;
MS(ESI):m/z calcd for[R3-2OTf]2+:1018.58;found:1018.93;elemental
analysis:Calcd (%) for C88H84N8O20F12S4Ru4:C 45.28,H 3.63,N 4.80;found:C 45.16,H
3.68,N 4.80。
Embodiment 4
The preparation of L2:Weigh bromobenzene 24.6g (105mmol), 17.5g (205mmol) imidazoles and 36.0g between 1,3-
100mL n,N-Dimethylformamide is added in 200mL eggplant-shape bottles in (260mmol) potassium carbonate, nitrogen is replaced three times, at 150 DEG C
Under the conditions of react 48h.Crude product crosses diatomite, and dichloromethane washing merges organic phase, washing then is added three times, saturation food
Three times, anhydrous sodium sulfate drying, solvent is spin-dried for obtaining solid and be washed with pentane, leaked using cloth salt water washing with Rotary Evaporators
Yellow solid is obtained by filtration in bucket, and crude product carries out column chromatography (solvent:Ethyl acetate) to obtain white solid be target product.
Preparing for A1 is in the same manner as in Example 1.
Accurate weighing ligand L 2 (2.1mg, 0.01mmol) is catalyzed with metal acceptor A1 (8.6mg, 0.01mmol) in 8mL
It in bottle, is dissolved, is stirred at room temperature for 24 hours using methanol, solvent, which is blown to 0.2mL, is added ether, uses centrifuge (2500r/
Min 10min) is centrifuged, supernatant liquor is discarded, then washed once with ether, obtains metal rectangular super molecular compound containing ruthenium R4.
Structural characterization is carried out to metal rectangular super molecular compound containing ruthenium R4:
1H NMR(400MHz,CD3OD)δ8.35(s,4H,H2-imidazole),7.74(s,4H,H5-imidazole),7.47–
7.35(m,8H,Ph),6.64(s,4H,H4-imidazole), 5.98 (d, J=6.2Hz, 8H, Php-cymene), 5.83 (d, J=
6.2Hz,8H,Php-cymene),2.92–2.76(m,4H,CH),2.26(s,12H,CH3), 1.37 (d, J=6.9Hz, 24H, CH
(CH3)2);
13C NMR(100MHz,CD3OD)δ172.4,139.1,137.7,133.3,130.8,121.2,120.8,112.5,
102.7,99.2,83.7,81.9,32.5,22.6,18.2;
MS(ESI):m/z calcd for[R4-2OTf]2+:918.05;found:917.96;elemental
analysis:Calcd (%) for C72H76N8O20F12S4Ru4:C 40.52,H 3.59,N 5.25;found:C 40.53,H
3.50,N 5.19。
Embodiment 5
Preparing for A2 is in the same manner as in Example 2, and preparing for L2 is same as Example 4.
Accurate weighing ligand L 2 (2.1mg, 0.01mmol) is catalyzed with metal acceptor A2 (9.1mg, 0.01mmol) in 8mL
It in bottle, is dissolved, is stirred at room temperature for 24 hours using methanol, solvent, which is blown to 0.2mL, is added ether, uses centrifuge (2500r/
Min 10min) is centrifuged, supernatant liquor is discarded, then washed once with ether, obtains metal rectangular super molecular compound containing ruthenium R5.
Structural characterization is carried out to metal rectangular super molecular compound containing ruthenium R5:
1H NMR(400MHz,CD3OD)δ8.47(s,4H,H2-imidazole),7.66(s,4H,H5-imidazole),7.65–
7.61(m,2H,Ph),7.51–7.39(m,6H,Ph),6.75(s,4H,H4-imidazole), 6.04 (d, J=6.2Hz, 8H,
Php-cymene), 5.85 (d, J=6.3Hz, 12H, Php-cymene),5.83(s,4H,Hdobq),2.92–2.78(m,4H,CH),2.24
(s,12H,CH3), 1.34 (d, J=6.9Hz, 24H, CH (CH3)2);
13C NMR(100MHz,CD3OD)δ185.3,140.0,138.1,132.9,131.0,121.7,121.3,114.9,
104.1,102.6,100.4,85.0,82.3,32.6,22.6,18.4;
MS(ESI):m/z calcd for[R5-2OTf]2+:968.56;found:968.10;elemental
analysis:Calcd (%) for C80H80N8O20F12S4Ru4:C 43.01,H 3.61,N 5.02;found:C 42.91,H
3.50,N 5.09。
Embodiment 6
Preparing for A3 is in the same manner as in Example 3, and preparing for L2 is same as Example 4.
Accurate weighing ligand L 2 (2.1mg, 0.01mmol) is catalyzed with metal acceptor A3 (9.6mg, 0.01mol) in 8mL
It in bottle, is dissolved, is stirred at room temperature for 24 hours using methanol, solvent, which is blown to 0.2mL, is added ether, uses centrifuge (2900r/
Min 10min) is centrifuged, supernatant liquor is discarded, then washed once with ether, obtains metal rectangular super molecular compound containing ruthenium R6.
Structural characterization is carried out to metal rectangular super molecular compound containing ruthenium R6:
1H NMR(400MHz,CD3OD)δ8.44(s,4H,H2-imidazole),7.61(s,2H,Ph),7.56(s,4H,
H5-imidazole),7.53–7.39(m,4H,Ph),7.19(s,8H,Hdonq),6.89(s,4H,H4-imidazole), 5.86 (d, J=
6.2Hz,8H,Php-cymene), 5.62 (d, J=6.2Hz, 8H, Php-cymene), 2.90-2.74 (m, 4H, CH), 2.13 (d, J=
4.6Hz,12H,CH3),1.40–1.26(m,24H,CH(CH3)2);
13C NMR(100MHz,CD3OD)δ172.3,139.1,138.5,138.4,132.8,130.7,123.4,121.6,
121.0,120.2,114.5,112.8,104.0,101.4,86.1(2),82.8,32.1,22.5,17.6;
MS(ESI):m/z calcd for[R4-2OTf]2+:1018.59;found:1018.96;elemental
analysis:Calcd (%) for C88H84N8O20F12S4Ru4:C 45.28,H 3.63,N 4.80;found:C 45.03,H
3.62,N 4.73。
Embodiment 7
The preparation of L3:Weigh a tribromo-benzene 24.6g (105mmol), 17.5g (205mmol) imidazoles and 36.0g
100mL n,N-Dimethylformamide is added in 200mL eggplant-shape bottles in (260mmol) potassium carbonate, nitrogen is replaced three times, at 150 DEG C
Under the conditions of react 48h.Crude product crosses diatomite, and dichloromethane washing merges organic phase, washing then is added three times, saturation food
Three times, anhydrous sodium sulfate drying, solvent is spin-dried for obtaining solid and be washed with pentane, leaked using cloth salt water washing with Rotary Evaporators
Yellow solid is obtained by filtration in bucket, and crude product carries out column chromatography (solvent:Ethyl acetate) to obtain white solid be target product.
Preparing for A1 is in the same manner as in Example 1.
(12.9mg, 0.015mmol are urged accurate weighing ligand L 3 (2.8mg, 0.010mmol) in 8mL with metal acceptor A1
Change in bottle, uses DCM/MeOH (v:V=1:1) it dissolves, stirs at room temperature for 24 hours, solvent, which is blown to 0.2mL, is added ether, makes
10min is centrifuged with centrifuge (2900r/min), discards supernatant liquor, then washed once with ether, metal triangular prism is obtained and contains ruthenium
Super molecular compound R7.
Structural characterization is carried out to metal triangular prism super molecular compound containing ruthenium R7:
1H NMR(400MHz,CD3OD:DMSO-d6v:V=1:1):δ8.51(s,6H,H2-imidazole),8.03(s,6H,
H5-imidazole),7.79(s,6H,Ph),6.78(s,6H,H4-imidazloe), 6.1 (d, J=5.7Hz, 12H, Hp-cymene),5.92
(d, J=5.9Hz, 12H, Hp-cymene),2.99–2.85(m,6H,CH),2.33(s,18H,CH3), 1.44 (d, J=6.9Hz,
36H,CH(CH3)2);
13C NMR(400MHz,CD3OD:DMSO-d6v:V=1:1):δ=172.50,139.66,139.06,131.10,
123.37,121.37,121.38,120.19,102.84,99.41,83.71,32.45,22.65,18.26;
MS(ESI):m/z calcd for[R7-2OTf]2+:1412.53;found:1412.34;elemental
analysis:Calcd (%) for C102H108N12O30F18S6Ru6:C 39.23,H 3.49,N 5.38;found:C 39.66,H
3.38,N5.33。
Embodiment 8
Preparing for A2 is in the same manner as in Example 2, and preparing for L3 is same as Example 7.
Accurate weighing ligand L 3 (2.8mg, 0.010mmol) is with metal acceptor A2 (13.6mg, 0.015mmol) in 8mL
It is catalyzed in bottle, uses DCM/MeOH (v/v=1:1) it dissolving, stirs at room temperature for 24 hours, solvent, which is blown to 0.2mL, is added ether,
10min is centrifuged using centrifuge (2900r/min), supernatant liquor is discarded, then washed once with ether, obtains metal triangular prism and contain
Ruthenium super molecular compound R8.
Structural characterization is carried out to metal triangular prism super molecular compound containing ruthenium R8:
1H NMR(400MHz,CD3OD):δ8.86(s,6H,H2-imidazole),7.89(s,6H,H5-imidazole),7.81(s,
6H,Ph),6.74(s,6H,H4-imidazole), 6.08 (d, J=6.2Hz, 12H, Hp-cymene), 5.85 (d, J=6.2Hz, 12H,
Hp-cymene),5.9(s,6H,Hdobq),2.94–2.82(m,6H,CH),2.25(s,18H,CH3), 1.36 (d, J=6.9Hz,
36H,CH(CH3)2);
13C NMR(100MHz,CD3OD):δ=185.3,140.0,139.1,130.7,121.2,120.1,111.8,
104.2,102.7,100.8,85.0,82.1,32.6,22.6,18.4;
MS(ESI):m/z calcd for[R8-2OTf]2+:1487.55;found:1488.13;elemental
analysis:Calcd (%) for C114H114N12O30F18S6Ru6:C 41.83,H 3.51,N 5.14;found:C 41.31,H
3.47,N4.93。
Embodiment 9
Preparing for A3 is in the same manner as in Example 3, and preparing for L3 is same as Example 7.
Accurate weighing ligand L 3 (2.8mg, 0.010mmol) is with metal acceptor A3 (14.4mg, 0.015mmol) in 8mL
It is catalyzed in bottle, uses DCM/CD3OD (v/v=1:1) it dissolving, stirs at room temperature for 24 hours, solvent, which is blown to 0.2mL, is added ether,
10min is centrifuged using centrifuge (2900r/min), supernatant liquor is discarded, then washed once with ether, obtains metal triangular prism and contain
Ruthenium super molecular compound R9.
Structural characterization is carried out to metal triangular prism super molecular compound containing ruthenium R9:
1H NMR(400MHz,CD3OD):δ8.74(s,6H,H2-imidazole),7.76(s,6H,H5-imidazole),7.74(s,
6H,Ph),7.25(s,12H,Hdonq),6.90(s,6H,H4-imidazole), 5.89 (d, J=5.9Hz, 12H, Hp-cymene),5.67
(d, J=5.9Hz, 12H, Hp-cymene),2.87–2.76(m,6H,CH),2.14(s,18H,CH3), 1.32 (d, J=6.9Hz,
36H,CH(CH3)2);
13C NMR(100MHz,CD3OD):δ=170.7,137.8,137.7,137.1,128.8,121.9,119.3,
118.8,111.2,109.7,102.5,100.5,85.0,81.1,30.7,21.2,16.3;
MS(ESI):m/z calcd for[R7-2OTf]2+:1562.58;found:1562.28;elemental
analysis:Calcd (%) for C126H120N12O30F18S6Ru6:C 44.21,H 3.53,N 4.91;found:C 44.71,H
3.59,N4.73。
Embodiment 10
The preparation of L4:Weigh bromobenzene, 12.1g (102mmol) benzimidazoles and 14.3g between 1, the 3- of 9.8g (42mmol)
100mL DMSO are added in 200mL eggplant-shape bottles in (104mmol) potassium carbonate, and displacement nitrogen three times, reacts under the conditions of 150 DEG C
48h.Crude product crosses diatomite, and then dichloromethane washing is extracted with methylene chloride/water, merge organic phase, and anhydrous sodium sulfate is dry
It is dry, it is spin-dried for being washed with pentane after solvent that yellow solid is obtained by filtration, crude product carries out column chromatography (EA) and obtains white solid.
Preparing for A1 is in the same manner as in Example 1.
It weighs ligand L 4 (3.1mg, 0.01mmol) and is catalyzed bottle in 8mL with metal acceptor A1 (8.6mg, 0.01mmol)
In, dissolved using methanol, stir at room temperature for 24 hours, by solvent be blown to 0.2mL be added ether, using centrifuge (2900r/min) from
Heart 10min discards supernatant liquor, then washed once with ether, obtains metal rectangular super molecular compound containing ruthenium R10.
Structural characterization is carried out to metal rectangular super molecular compound containing ruthenium R10:
1H NMR(400MHz,CD3OD):δ=8.59 (s, 4H, H2-imidazole), 7.72 (d, J=8.2Hz, 4H,
H7-imidazole), 7.64-7.58 (m, 2H, Ph), 7.54 (d, J=8.5Hz, 4H, H4-imidazole), 7.37 (t, J=7.8Hz,
6H, Ph), 7.32 (d, J=8.3Hz, 4H, H5-imidazole), 7.12 (t, J=7.7Hz, 4H, H6-imidazole), 6.11 (d, J=
5.5Hz,4H,Php-cymene), 5.98 (d, J=5.6Hz, 4H, Php-cymene), 5.92 (d, J=5.7Hz, 4H, Php-cymene),
5.88 (d, J=5.5Hz, 4H, Php-cymene),2.99–2.82(m,4H,CH),2.13(s,12H,CH3), 1.40 (dd, J=
30.9,6.7Hz,24H,CH(CH3)2);
13C NMR(100MHz,CD3OD):δ=185.3,140.0,139.1,130.6,123.3,121.2,111.8,
104.2,102.7,100.7,85.0,82.1,32.6,22.6,18.4;
MS(ESI):m/z calcd for[R10-2OTf]2+:1018.58;found:1018.49;elemental
analysis:Calcd (%) for C88H84N8O20F12S4Ru4:C 45.28,H 3.63,N 4.80;found:C 44.53,H
3.60,N 4.93。
Embodiment 11
Preparing for A2 is in the same manner as in Example 2, and preparing for L4 is same as in Example 10.
Accurate weighing ligand L 4 (3.1mg, 0.01mmol) is catalyzed with metal acceptor A2 (9.1mg, 0.01mmol) in 8mL
It in bottle, is dissolved, is stirred at room temperature for 24 hours using methanol, solvent, which is blown to 0.2mL or so, is added ether, uses centrifuge
(2900r/min) centrifuges 10min, discards supernatant liquor, then washed once with ether, obtains the metal rectangular chemical combination of supermolecule containing ruthenium
Object R11.
Structural characterization is carried out to metal rectangular super molecular compound containing ruthenium R11:
1H NMR(400MHz,CD3OD):δ=8.75 (s, 4H, H2-imidazole),7.90–7.79(m,4H,H7-imidazole),
7.77-7.70 (s, 2H, Ph), 7.61 (d, J=8.3Hz, 4H, H4-imidazole), 7.58-7.45 (m, 6H, Ph), 7.33 (t, J=
7.8Hz,4H,H5-imidazole),7.04(s,4H,H6-imidazole), 6.14 (d, J=6.4Hz, 8H, Php-cymene),5.91(d,J
=6.2Hz, 8H, Php-cymene),5.71(s,4H,Hdobq),2.96–2.82(m,4H,CH),2.13(s,12H,CH3),1.34
(d, J=6.9Hz, 24H, CH (CH3)2);
13C NMR(100MHz,CD3OD):δ=185.1,146.3,141.3,137.3,133.3,126.9,126.4,
125.5,123.4,120.2,119.5,113.1,105.6,102.3,100.4,84.5,82.3,32.7,22.6,18.6;
MS(ESI):m/z calcd for[R11-2OTf]2+:1068.63;found:1068.48;elemental
analysis:Calcd (%) for C96H88N8O20F12S4Ru4:C 47.37,H 3.64,N 4.60;found:C 47.00,H
3.59,N 4.64。
Embodiment 12
Preparing for A3 is in the same manner as in Example 3, and preparing for L4 is same as in Example 10.
Accurate weighing ligand L 4 (3.1mg, 0.01mmol) is catalyzed with metal acceptor A3 (9.9mg, 0.01mmol) in 8mL
It in bottle, is dissolved, is stirred at room temperature for 24 hours using methanol, solvent, which is blown to 0.2mL or so, is added ether, uses centrifuge
(2900r/min) centrifuges 10min, discards supernatant liquor, then washed once with ether, obtains the metal rectangular chemical combination of supermolecule containing ruthenium
Object R12.
Structural characterization is carried out to metal rectangular super molecular compound containing ruthenium R12:
1H NMR(400MHz,CD3OD):δ=8.66 (s, 4H, H2-imidazole), 7.86 (t, J=8.1Hz, 2H, Ph),
7.80 (d, J=8.3Hz, 4H, H7-imidazole), 7.64 (s, 2H, Ph), 7.40 (d, J=8.4Hz, 4H, H4-imidazole),
7.37-7.28 (m, 4H, Ph), 7.25 (t, J=7.8Hz, 4H, H5-benzimidazole),7.13(s,8H,Hdonq),6.69(s,4H,
H6-imidazole), 5.93 (d, J=6.0Hz, 8H, Php-cymene), 5.67 (d, J=6.0Hz, 8H, Php-cymene),2.91–2.80
(m,4H,CH),2.01(s,12H,CH3), 1.29 (d, J=6.9Hz, 24H, CH (CH3)2);
13C NMR(100MHz,CD3OD):δ=172.0,145.0,141.8,138.3,137.4,133.6,132.9,
126.4,126.1,124.9,119.6,118.2,113.0,112.6,105.1,101.3,85.6,83.1,32.1,22.6,
18.0;
MS(ESI):m/z calcd for[R12-2OTf]2+:1118.62;found:1118.49;elemental
analysis:Calcd (%) for C104H92N8O20F12S4Ru4:C 49.29,H 3.66,N 4.42;found:C 49.01,
H4.40,N 4.28。
Embodiment 13
The preparation of L5:Catechol (4.4g, 40mmol) is weighed, the stirring of 50mL N,N-dimethylformamides, which is added, makes it
Dissolving, is slowly added to Anhydrous potassium carbonate (23.2g, 168mmol), stirs and 9.4mL, 12.1g, 88mmol are added after 30min, and ρ=
Nucleophilic substitution 18h occurs at 90 DEG C for 1.28g/mL (25 DEG C) bromination of n-butane, is extracted, is associated with water/ethyl acetate
Then machine phase, the washing of NaOH aqueous solutions use saturated common salt water washing three times three times, anhydrous sodium sulfate drying, Rotary Evaporators rotation
Dry solvent obtains 1,2- Dibutoxy Benzenes.1,2- Dibutoxy Benzenes (4.0g, 18.0mmol) are dissolved in 40mL acetic acid, in ice bath
Lower stirring makes reaction system be cooled to 0 DEG C, measures 3.5mL nitric acid and 30mL fuming nitric aicds, is leaked after mixing with constant pressure addition
Bucket is slowly dropped into system, and reaction solution remains at 0 DEG C or so.After being added dropwise, ice bath is removed, reaction temperature is made to be restored to
Room temperature, stirring 4h occur nitration reaction, pour into mixture of ice and water after the completion, there is yellow solid precipitation, wait for ice melting, progress
It filters, massive laundering is used in combination to wash.Solid is collected, 80mL absolute ethyl alcohols reflux 0.5h is added and delays after yellow solid all dissolving
Slow cool down is precipitated yellow crystals, filters again, collects solid, weighs nitration product (4.0g, 12.8mmol), Pd/C catalyst
The dissolving of 40mL absolute ethyl alcohols is added in 100mL eggplant type bottles in (90mg).Ventilation 3 times is vacuumized, is then added rapidly to reaction system
Enter 6.3mL hydrazine hydrates, reacted at 80 DEG C and reduction reaction occurs overnight, waits for that reaction system is cooled to room temperature, it is rapid to cross diatomite
Except the solid kind by-product generated in dereaction, dry solvent is hanged using Rotary Evaporators, obtains yellow solid, 50mL first is added
Acid vacuumizes ventilation, reflux, and cyclization occurs and is reacted overnight at imidazoles, most of formic acid is removed in then vacuum distillation, is then used
PH value in reaction is adjusted to neutrality by ammonium hydroxide, saturated sodium carbonate solution, then makes to be extracted with ethyl acetate, and merges organic phase, washing three
Secondary, saturated common salt water washing hangs dry solvent three times, using Rotary Evaporators, and ether is added and washs and is filtered using cloth funnel,
Obtain 5,6- dibutoxy benzo imidazoles.It weighs to bromobenzene (11.8g, 50.4mmol), 5,6- dibutoxy benzo imidazoles
(32.1g, 122.4mmol), potassium carbonate (17.2g, 124.8mmol) and copper oxide (0.5g, 6.0mmol) are in 200mL eggplant shapes
Bottle, is added 60mL n,N-Dimethylformamide, and three times, Liv Ullmann (Ullmann) occurs under the conditions of 150 DEG C for displacement nitrogen anti-
Answer 48h.Crude product crosses diatomite, and dichloromethane washing merges organic phase, washing then is added three times, saturated common salt water washing
Three times, anhydrous sodium sulfate is dried, and solvent is spin-dried for obtaining solid and be washed with pentane with Rotary Evaporators, is filtered using cloth funnel
To white solid, crude product carries out column chromatography (ethyl acetate) and obtains white solid to be target product.
L5 made from embodiment 13 is characterized, Fig. 1 is1HNMR spectrograms, Fig. 2 are13C NMR spectras, can by Fig. 1~2
To find out, L5 obtained have shown in structure.
The preparation method of A1 is in the same manner as in Example 1.
Accurate weighing ligand L 5 (6.0mg, 0.01mmol) is catalyzed with metal acceptor A1 (8.6mg, 0.01mmol) in 8mL
It in bottle, is dissolved, is stirred at room temperature for 24 hours using methanol, solvent, which is blown to 0.2mL, is added ether, uses centrifuge (2900r/
Min 10min) is centrifuged, supernatant liquor is discarded, then washed once with ether, obtains metal rectangular super molecular compound containing ruthenium R13.
Structural characterization is carried out to metal rectangular super molecular compound containing ruthenium R13:
1H NMR(400MHz,CD3OD)major conformational isomer:δ=8.32 (s, 4H,
H2-imidazole),7.56(s,8H,Ph),6.99(s,4H,H7-imidazole),6.71(s,4H,H4-imidazole),5.98–5.91(m,
8H,Php-cymene),5.78–5.72(m,8H,Php-cymene),4.24–4.10(m,8H,H1-butyl), 3.98 (t, J=6.3Hz,
8H,H1-butyl),2.92–2.82(m,4H,CH),2.20(s,12H,CH3),1.99–1.85(m,16H,H2-butyl),1.73–
1.59(m,16H,H3-butyl), 1.41 (d, J=6.9Hz, 12H, CH (CH3)2), 1.36 (d, J=6.9Hz, 12H, CH (CH3)2),
1.12 (t, J=7.4Hz, 12H, CH2CH3), 1.06 (t, J=7.4Hz, 12H, CH2CH3);
13C NMR(100MHz,CD3OD):δ=173.2,171.9,151.3,149.9,143.1,135.4,135.3,
126.9,126.2,103.6,102.4,98.7,95.5,83.2,82.9,82.4,82.0,70.8,70.5,32.8,32.7(2),
22.8,22.5,20.6,20.5,18.4,14.5(2);
MS(ESI):m/z calcd for[R13-2OTf]2+:1306.81;found:1306.62;elemental
analysis:Calcd (%) for C120H148N8O28F12S4Ru4:C 49.51,H 5.12,N 3.85;found:C 49.22,H
5.13,N 3.75。
Embodiment 14
Preparing for A2 is in the same manner as in Example 2, and the preparation of L5 is identical as embodiment 13.
Accurate weighing ligand L 5 (6.0mg, 0.01mmol) is catalyzed with metal acceptor A2 (9.1mg, 0.01mmol) in 8mL
It in bottle, is dissolved, is stirred at room temperature for 24 hours using methanol, solvent, which is blown to 0.2mL, is added ether, uses centrifuge (2900r/
Min 10min) is centrifuged, supernatant liquor is discarded, then washed once with ether, obtains metal rectangular super molecular compound containing ruthenium R14.
Structural characterization is carried out to metal rectangular super molecular compound containing ruthenium R14:
1H NMR(400MHz,CD3OD)major conformational isomer:δ=8.36 (s, 4H,
H2-imidazole),7.72(s,8H,Ph),7.07(s,4H,H7-imidazole),7.00(s,8H,H4-imidazole),6.14–6.06(m,
8H,Php-cymene),5.85(m,8H,Php-cymene),5.62(s,4H,Hdobq),4.04–3.97(m,8H,H1-butyl),3.96–
3.88(m,8H,H1-butyl),3.01–2.85(m,4H,CH),2.15(s,12H,CH3),1.84–1.70(m,16H,H2-butyl),
1.60–1.45(m,16H,H3-butyl), 1.36 (d, J=6.9Hz, 24H, CH (CH3)2), 0.98 (t, 24H, J=6.1Hz,
CH2CH3);
13C NMR(100MHz,CD3CN):δ=185.2,150.3,149.4,143.3,135.7,135.3,127.4,
127.3,123.7,120.5,104.8,103.1,102.1,101.7,99.4,96.4,83.9,82.6,82.3,70.1,32.4,
31.9,22.7,22.4,20.0(2),18.7,14.7;
MS(ESI):m/z calcd for[R14-2OTf]2+:1356.83;found:1356.66;elemental
analysis:Calcd (%) for C128H152N8O28F12S4Ru4:C 51.06,H 5.09,N 3.72;found:C 50.98,H
5.11,N 3.75。
Embodiment 15
Preparing for A3 is in the same manner as in Example 3, and the preparation of L5 is identical as embodiment 13.
Accurate weighing ligand L 5 (6.0mg, 0.01mmol) is catalyzed with metal acceptor A3 (9.9mg, 0.01mmol) in 8mL
It in bottle, is dissolved, is stirred at room temperature for 24 hours using methanol, solvent, which is blown to 0.2mL or so, is added ether, uses centrifuge
(2900r/min) centrifuges 10min, discards supernatant liquor, then washed once with ether, obtains the metal rectangular chemical combination of supermolecule containing ruthenium
Object R15.
Structural characterization is carried out to metal rectangular super molecular compound containing ruthenium R15:
1H NMR(400MHz,CD3CN)major conformational isomer:δ=8.05 (s, 4H,
H2-imidazole),7.63(s,8H,Ph),7.20(s,4H,H7-imidazole),7.08(s,8H,Hdobq),6.86(s,4H,
H4-imidazole),5.79–5.70(m,8H,Php-cymene), 5.56 (d, J=6.1Hz, 8H, Php-cymene),4.15–4.04(m,
8H,H1-butyl),3.96–3.86(m,8H,H1-butyl),2.93–2.80(m,4H,CH),2.08(s,12H,CH3),1.86–1.75
(m,8H,H2-butyl),1.74–1.61(m,8H,H2-butyl),1.57–1.50(m,8H,H3-butyl),1.48–1.36(m,8H,
H3-butyl), 1.31 (d, J=7.1Hz, 24H, CH (CH3)2), 1.10 (t, J=7.0Hz, 12H, CH2CH3), 1.00 (t, J=
7.4Hz,12H,CH2CH3);
13C NMR(100MHz,CD3CN):δ=172.5,170.6,149.9,149.2,142.7,138.3,138.1,
135.7,135.3,127.6,127.1,123.7,120.5,112.4,104.5,101.9,100.4,96.2,84.9,83.6,
83.3,70.0,32.0,31.9,31.7,22.7,22.3,20.0,17.8,14.2(2);
MS(ESI):m/z calcd for[R13-2OTf]2+:1406.86;found:1406.64.elemental
analysis:Calcd (%) for C136H156N8O28F12Ru4S4:C 52.50,H 5.05N 3.60;found:C 52.43,H
5.10,N 3.50。
Embodiment 16
The preparation method of L6 is similar with the preparation method of L5 in embodiment 13, differs only in and replaces bromine with n-octane bromide
For normal butane.
L6 made from embodiment is characterized, Fig. 3 is1HNMR spectrograms, Fig. 4 are13C NMR spectras, can be with by Fig. 3~4
Find out, L6 obtained have shown in structure.
Preparing for A1 is in the same manner as in Example 1.
Accurate weighing ligand L 6 (8.2mg, 0.01mmol) is catalyzed with metal acceptor A1 (8.6mg, 0.01mmol) in 8mL
It in bottle, is dissolved, is stirred at room temperature for 24 hours using methanol, solvent, which is blown to 0.2mL, is added ether, uses centrifuge (2900r/
Min 10min) is centrifuged, supernatant liquor is discarded, then washed once with ether, obtains metal rectangular super molecular compound containing ruthenium R16.
Metal rectangular super molecular compound containing ruthenium R16 is characterized:
1H NMR(400MHz,CD3OD):δ=8.31 (s, 4H, H2-imidazole),7.55(s,8H,Ph),6.98(s,4H,
H7-imidazole),6.70(s,4H,H4-imidazole),5.97–5.89(m,8H,Php-cymene), 5.74 (d, J=6.3Hz, 8H,
Php-cymene),4.02–3.83(m,16H,H1-nonyl),2.92–2.80(m,4H,CH),2.19(s,12H,CH3),1.99–1.85
(m,16H,H2-nonyl),1.74–1.56(m,16H,H3-nonyl),1.50–1.32(m,88H,H4,5,6,7-nonyl,CH(CH3)2),
1.01–0.91(m,24H,CH2CH3);
13C NMR(100MHz,CD3OD):δ=151.4,149.9,143.0,135.4,135.3,126.9,126.2,
103.7,102.5,98.7,95.5,83.2,82.9,82.4,82.0,71.1,70.8,33.3,33.2,32.7,31.0(2),
30.9,30.8,30.7,27.6,27.5,23.9(2),22.8,22.5,18.4,14.6(2);
MS(ESI):m/z calcd for[R17-2OTf]2+:1531.06;found:1530.81;elemental
analysis:Calcd (%) for C152H212N8O28F12Ru4S4:C 54.34,H 6.36,N 3.34;found:C 54.04,H
6.34,N 3.26。
Embodiment 17
Preparing for A2 is in the same manner as in Example 2, and the preparation of L6 is identical as embodiment 16.
Accurate weighing ligand L 6 (8.2mg, 0.01mmol) is catalyzed with metal acceptor A2 (9.1mg, 0.01mmol) in 8mL
It in bottle, is dissolved, is stirred at room temperature for 24 hours using methanol, solvent, which is blown to 0.2mL, is added ether, uses centrifuge (2900r/
Min 10min) is centrifuged, supernatant liquor is discarded, then washed once with ether, obtains metal rectangular super molecular compound containing ruthenium R17.
Structural characterization is carried out to metal rectangular super molecular compound containing ruthenium R17:
1H NMR(400MHz,CD3OD)major conformational isomer:δ=8.37 (s 4H,
H2-imidazole),7.79(s,8H,Ph),7.04(s,4H,H7-imidazole),6.94(s,4H,H4-imidazole),6.10(s,8H,
Phphenyl), 5.87 (d, J=8.0Hz, 8H, Php-cymene),5.60(s,4H,Hdobq),4.16–4.03(m,8H,H1-nonyl),
4.03–3.96(m,8H,H1-nonyl),3.00–2.86(m,4H,CH),2.16(s,12H,CH3),1.91–1.81(m,8H,
H2-nonyl),1.81–1.73(m,8H,H2-nonyl),1.62–1.53(m,8H,H3-nonyl),1.53–1.46(m,8H,H3-nonyl),
1.44–1.20(m,88H,H4,5,6,7,8-nonyl,CH(CH3)2),0.97–0.81(m,24H,CH2CH3);
13C NMR(100MHz,CD3CN):δ=185.2,184.7,150.3,149.4,143.1,135.6,135.2,
127.5,125.8,104.7,103.0,102.1,101.7,99.4,96.4,84.1,83.9,82.7,82.2,70.2,66.3,
32.7,32.4,30.3,30.2,30.1,29.9,26.9(2),26.8,23.5,22.7,22.4,18.7,14.5;
MS(ESI):m/z calcd for[R16-2OTf]2+:1581.08;found:1581.84;elemental
analysis:Calcd (%) for C160H216N8O28F12S4Ru4:C 55.45,H 6.29,N 3.24;found:C 54.94,H
6.24,N 3.20。
Application examples
To the R1~17 of super molecular compound containing ruthenium made from the embodiment of the present invention and unassembled ligand and acceptor into
Row MTT experiment, to verify whether they have active anticancer.It takes and freezes cancer cell HCT-116 (human colon cancer cell), A549 (people
Lung carcinoma cell) it is placed in water-bath, it recovers at 37 DEG C.Using DMEM medium culture HCT-116 cells, cultivated using F-12K
Base culture A549 cells.10% heat fire extinguishing fetal calf serum (FBS) and 1% penicillin-chain are added in all culture mediums used
Mycin solution.Cancer cell culture contains CO at 37 DEG C2In 5% cell incubator.Micro- sem observation cell growth is used daily
Situation, two kinds of cancer cells start to test after passing on for 3 generations.
Ruthenium super molecular compound R1~17 will be contained and control drug adriamycin and Platinol cisplatin is dissolved in DMSO is made into 5mg respectively
mL-1It is spare that stoste is stored in -20 DEG C of refrigerators.Cancer cell suspension is transferred to liquid-transfering gun in 96 orifice plates, per hole cell quantity control
System is 0.5 × 104~1.0 × 104A, orifice plate cultivates 12/24h in advance in incubator, and drug stoste is added in culture medium, and
And gradient dilution, then using the culture solution containing drug, (DMSO concentration is in culture solution Zhong <0.5%) culture of orifice plate Central Plains is replaced
Liquid, cell are 48h with the drug response time.
It waits for that after reaction, MTT being fitted in the phosphate buffer solution (PBS) of pH=7.2, uses the micropore mistake of 0.22M
Filter filters (process for preparation, which should be noted that, to be protected from light).The MTT solution of 20L is added per hole, 4h is cultivated in incubator.It moves after reaction
Solution in orifice plate is walked, 100L DMSO are added in every hole, orifice plate placement shaking table is waved into 30min, uses microplate reader test suction later
Luminosity (λ=492nm), then with hundred of the contribution ratios calculating survivaling cell with cell and negative control group after drug effect
Divide ratio.Finally IC is determined using the logarithm percentage of linear regression Function Fitting survivaling cell and drug concentration50Value, as a result such as
Shown in table 1, super molecular compound containing ruthenium R3, R6, R9 and R12 effects are better.
1 IC of table50Test result
Survival rate=(control group A value-processing hole A values)/(control group A value-blank group A values) × 100%
Inhibiting rate=(1- survival rates) × 100%
lgIC50=Xm-I (P- (3-Pm-Pn)/4)
Xm:Lg maximum doses;
I:Lg (maximum dose/adjacent dosage);
P:The sum of positive reaction rate;
Pm:Maximum positive reaction rate;
Pn:Minimum positive reaction rate.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. benzimidazole ligand, which is characterized in that shown in its structural formula such as following formula (I):
Wherein, R n-C4H9O or n-C8H17O。
2. the synthetic method of benzimidazole ligand described in claim 1, which is characterized in that including step:
(1) dust technology and fuming nitric aicd are added drop-wise in the acetic acid solution of 1,2- dialkoxy benzenes and nitration reaction occurs, obtain nitre
Change product, 1, the 2- dialkoxy benzenes are 1,2- Dibutoxy Benzenes or 1, bis- octyloxy benzene of 2-;
(2) reduction reaction occurs for nitration product, Pd/C catalyst, absolute ethyl alcohol and the hydrazine hydrate mixing obtained step (1),
Obtain reduzate;
(3) reduzate that step (2) obtains is mixed into generation cyclization with formic acid and reacts into imidazole ring, obtain benzimidazole derivatess
Object, the benzimidizole derivatives are 5,6- dibutoxy benzo imidazoles or 5, bis- octyloxy benzimidazoles of 6-;
(4) benzimidizole derivatives that obtain step (3), mixed to bromobenzene, potassium carbonate, copper oxide and N,N-dimethylformamide
It closes and ullmann reaction occurs, obtain benzimidazole ligand.
3. super molecular compound containing ruthenium, which is characterized in that shown in its structural formula such as following formula (II),
Wherein, A is the compound with structure shown in following formula A1, A2 or A3,
L is the compound with structure shown in formula (I) described in formula L1, L2, L4 or claim 1,
4. super molecular compound containing ruthenium, which is characterized in that shown in its structural formula such as following formula (III),
Wherein, A is the compound of structure shown in following formula A1, A2 or A3,
L is the compound of structure shown in following formula L3,
5. the preparation method of the super molecular compound containing ruthenium described in claim 3 or 4, which is characterized in that including step:It will be described
Coordination driving self-assembling reaction occurs for compound A, the compound L and polar organic solvent mixing, obtains supermolecular containing ruthenium
Close object.
6. preparation method according to claim 5, which is characterized in that the polar organic solvent be dichloromethane and/or
Methanol.
7. preparation method according to claim 5, which is characterized in that the time of the coordination driving self-assembling reaction is 24
~48h.
8. preparation method according to claim 5, which is characterized in that the coordination drives self-assembling reaction last handling process
Including:Ether is added after driving the polar organic solvent in self-assembling reaction product to remove coordination and carries out centrifugal treating.
9. preparation method according to claim 8, which is characterized in that the rotating speed of the centrifugal treating is 2900rpm, described
The time of centrifugal treating is 10min.
10. application of the super molecular compound containing ruthenium described in claim 3 or 4 in preparing anticancer drug.
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| CN115141148A (en) * | 2021-03-15 | 2022-10-04 | 江苏师范大学 | Bisimidazole ligand, ruthenium supermolecule self-assembly compound with imidazole ligands with different alkoxy chains, preparation method and application |
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