CN109810147A - The benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label and preparation and application - Google Patents
The benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label and preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label, refer to using benzimidazole as skeleton, by axial ligand of pyridine prepared by pyrene label benzimidazole N-heterocyclic carbine porpezite metal complex, structural formula are as follows:
Description
Technical field
The present invention relates to the benzimidazole N-heterocyclic carbine porpezite metal complexes that catalysis technical field more particularly to pyrene mark
And it prepares and applies.
Background technique
Composition catalyst is a kind of complex constituted centered on transition metal, is in the transition metal of center
Atom, the electronics unsaturation with d track form metal-ligand chemical bond with ligand difference rail effect.Azacyclo- card
Guest (NHCs) is a kind of Novel Ligands with strong electron donation, compared with traditional Phosphine ligands, with intermetallic coordination
Mode is quite similar with organophosphorus ligand.But nitrogen heterocycle carbine ligand synthesizes simple, small toxicity, strong electron supplying capacity, in
The coordination ability of heart metal is strong, is especially that Phosphine ligands are incomparable to the characteristics of good stability of water, heat and air.
In recent years, the research in relation to N-heterocyclic carbine metal complex has become Coordinative Chemistry, organic chemistry, catalytic chemistry
One of the research hotspot in equal fields, especially in complex-catalyzed C-C, C-O, C-N coupling reaction of N-heterocyclic carbine palladium metal and
The fields such as the metal complex catalyzed olefin metathesis reaction of N-heterocyclic carbine ruthenium have achieved howling success (Chem. Rev.
2009,109, 3612-3676; Acc. Chem. Res. 2008, 41, 1440-1449; Angew. Chem., Int.
Ed. 2008, 47, 3122-3172; Coor. Chem. Rev. 2007, 251, 610-641; Angew. Chem.,
Int. Ed. 2007,46,2768-2813.).
Since the N-heterocyclic carbine metal complexes of different skeletons have respective special construction and reactivity worth, in order to
It can understand from many aspects, at many levels and explore their potential use and the application prospect in future, the nitrogen of Development of Novel structure
Heterocyclic carbene metal complex has very important meaning in fields such as Synthetic Organic Chemistry, catalytic chemistry, Organometallic Chemistries
Justice.For now, the N-heterocyclic carbine metal complex developed both at home and abroad, basic structural unit are based primarily upon five-membered ring
Imidazoles or the structures such as glyoxalidine, wherein the benzimidazole N-heterocyclic carbine metal complex as one of representative skeleton
Study it is less, still in its infancy.Such as: the 1,3 1 diisopropyl benzo imidazoles bromides of use such as Huynh and acetic acid handle, bromine
Change sodium reacts in dromisol solvent generates Cabbeen dimer, then uses the depolymerization of second eyeball, has obtained a kind of structure novel
Benzimidazole N-heterocyclic carbine porpezite metal complex, and be applied to catalysis Suzuki coupling reaction in
(Organometallics, 2006,25,3267-3274.).
α, β-unsaturation acetylenic ketone are important fine chemicals and medicine intermediate as a kind of carbonyls, are widely applied
In the synthesis of natural products, bioactive molecule, polyfunctional compound, heterocyclic compound and its derivative etc..In transition
Under metal complex catalytic action, using halogenated organic aromatic hydrocarbons, alkynes and CO cheap and easy to get as raw material, pass through Sonogashira
Carbonylation synthesizes α, and β-unsaturated aldehydes ketone compounds are a simple and direct and efficient routes, has atom economy, environment
The advantages that friendly and easy to operate.Palladium phosphine metal complex containing Phosphine ligands is catalysis Sonogashira carbonylation
Effective catalyst system, however these catalyst systems are both needed to add a large amount of toxic Phosphine ligands to stablize in Pd (0) catalytic activity
The heart, there is it is many it is unfavorable (Chem. Soc. Rev, 2011,4986-5009; Chem. Rev,2013,113, 192-
270.).Up to the present, there is not yet benzimidazolyl N-heterocyclic carbine metal complex is in Sonogashira carbonylation
Related application report.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of benzimidazole N-heterocyclic carbine palladium metals of pyrene label to match
Close object.
Another technical problem to be solved by this invention is to provide the benzimidazole N-heterocyclic carbine porpezite of pyrene label
The preparation method of metal complex.
Third technical problem to be solved by this invention is to provide the benzimidazole N-heterocyclic carbine porpezite of pyrene label
The application of metal complex.
To solve the above problems, the benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label of the present invention,
Be characterized in that: using benzimidazole as skeleton, by axial ligand of pyridine prepared by pyrene label benzimidazole N-heterocyclic carbine
Porpezite metal complex, structural formula are as follows:。
The preparation method of the benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label as described above, including following step
It is rapid:
(1) 1-(2- bromine oxethyl is synthesized) pyrene:
Using acetone as solvent, by 1- hydroxyl pyrene, cesium carbonate, 1,2- Bromofume 1:1.5 ~ 2.5:3.5 ~ 4.5 in molar ratio, in 60
~ 80 DEG C of heating reactions flow back 4 ~ 15 hours, isolate and purify product after reaction to get 1-(2- bromine oxethyl) pyrene；
(2) 1-(ethyoxyl is synthesized) pyrenyl benzimidazole:
Using acetonitrile as reaction dissolvent, by the 1-(2- bromine oxethyl) pyrene, benzimidazole, potassium hydroxide in molar ratio 1:1.3 ~
2.0:1.1 ~ 1.5 flow back 20 ~ 30 hours in 80 ~ 100 DEG C of heating reactions, isolate and purify product after reaction to get 1-(second
Oxygroup) pyrenyl benzimidazole；
(3) 1-(ethyoxyl is synthesized) pyrene -3- benzyl benzimidazole bromide:
Using acetonitrile as reaction dissolvent, under inert atmosphere, by the 1-(ethyoxyl) pyrenyl benzimidazole, benzyl bromide in molar ratio 1:
1.0 ~ 1.5, it flows back 20 ~ 30 hours in 80 ~ 100 DEG C of heating reactions.Isolate and purify product after reaction to get 1-(ethyoxyl)
Pyrene -3- benzyl benzimidazole bromide；
(4) the benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label is synthesized:
Using pyridine as reaction dissolvent, under inert atmosphere, by palladium chloride, the 1-(ethyoxyl) pyrene -3- benzyl benzimidazole bromine
Salt, potassium carbonate, potassium bromide 1:1.0 ~ 1.5:3 ~ 10:8 ~ 20 in molar ratio, are heated to reflux 20 ~ 30 hours, anti-in 80 ~ 100 DEG C
After answering, the benzimidazole N-heterocyclic carbine porpezite metal complex that product marks to get pyrene is isolated and purified after reaction.
Its synthesis process such as following formula:
。
The application of the benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label as described above, it is characterised in that: should
The benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label is as catalyst in iodo aromatic hydrocarbon, carbon monoxide (CO), end
In three component Sonogashira carbonylation of alkynes, one-step synthesis intermediate α, β-unsaturation acetylenic ketone；The benzimidazole nitrogen
The additional amount of heterocycle carbine porpezite metal complex be the iodo aromatic hydrocarbon mole 0.5 ~ 3 mol%, preferably 0.1 ~
0.25mol%。
Sonogashira carbonylation synthesizes α, and β-unsaturation acetylenic ketone reaction equation is as follows:
。
Wherein: carbon monoxide pressure is 0.5 ~ 3.0 MPa, preferably 1.0 ~ 2.0 MPa；An oxidation of high-purity is preferred
Carbon can add the mixed gas such as hydrogen, inert gas as long as not influencing to react.
Reaction temperature is 60 ~ 140 DEG C, preferably 80 ~ 100 DEG C；Reaction time is 6 ~ 30 h.
The structural formula of iodo aromatic hydrocarbon is；R in formula1Refer to methyl, methoxyl group, amino, fluorine, chlorine, fluoroform
One of base, formic acid esters, naphthalene.
Terminal alkyne structural formula are as follows:；R in formula2Refer to phenyl, 4- fluorophenyl, 4- bromophenyl, 4- methylbenzene
One of base, 4- ethylphenyl, 4- butyl phenyl, 4- tert-butyl-phenyl, 4- methoxyphenyl, 4- amoxy phenyl.
Reaction dissolvent refers to one of toluene, tetrahydrofuran, dioxane, acetonitrile, methyl phenyl ethers anisole.
Reaction alkali used refers to one of triethylamine, potassium carbonate, cesium carbonate, sodium acetate.
Compared with the prior art, the present invention has the following advantages:
1, reaction condition of the present invention is mild, technical process is easy, and convenient for operation, equipment requirement and reaction condition are easy to accomplish, fits
Preferably it is mass produced.
2, preparation method of the present invention is simple, and catalyst amount is small, and high catalytic efficiency.
3, the present invention is in the application of Sonogashira carbonylation, and the substrate scope of application is relatively wide, reaction mixture passes through
Simple post separation is crossed, energy high yield obtains high-purity alpha, β-unsaturation acetylenic ketone.
4, the results show, using benzimidazole N-heterocyclic carbine porpezite metal complex of the present invention as catalyst,
The selectivity height of Sonogashira carbonylation, high conversion rate.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is catalyst monocrystalline spectrogram of the present invention.
Fig. 2 is catalyst hydrogen nuclear magnetic spectrogram of the present invention.
Fig. 3 is catalyst carbon nucleus magnetic hydrogen spectrum figure of the present invention.
Fig. 4 is catalyst ultraviolet-visible spectrogram (concentration 1.26 × 10 of the present invention-5Mol/L).
Fig. 5 is catalyst fluorescence spectra (concentration 1.26 × 10 of the present invention-5Mol/L, excitation wavelength 386nm).
Specific embodiment
The benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label, refers to and is as skeleton, with pyridine using benzimidazole
The benzimidazole N-heterocyclic carbine porpezite metal complex of the label of pyrene prepared by axial ligand, structural formula are as follows:
。
The preparation method of the benzimidazole N-heterocyclic carbine porpezite metal complex of 1 pyrene of embodiment label, including following step
It is rapid:
(1) 1-(2- bromine oxethyl is synthesized) pyrene:
In 100mL dry round-bottomed flask, the acetone of 35mL, 1- hydroxyl pyrene (2.18g, 10 mmol), Cs are sequentially added2CO3
(6.5 g, 19.9 mmol) and 1,2- Bromofume (7.48 g, 39.8mmol), 60 DEG C of heating are reacted 6 hours.Liquid cooling to be reacted
But it to room temperature, adds methylene chloride and is repeatedly extracted with water.Anhydrous MgSO is added in organic phase4Dry, filtering, revolving.Finally use column
Chromatography method carries out separating-purifying (eluent: petroleum ether: methylene chloride=4:1) to product, finally obtains yellow solid 1-
(2- bromine oxethyl) pyrene (2.282 g, yield 70%).
1H NMR (400 MHz, CDCl3,298k): δ 8.49 (d,J = 9.2 Hz, 1H), 8.10 (m, 4H),
7.97 (m, 2H), 7.91 (d, J = 9.0 Hz, 1H), 7.51 (d, J = 8.4 Hz, 1H), 4.64 (t, J
= 6.2 Hz, 2H), 3.85 (t, J = 6.2 Hz, 2H).
13C NMR (101 MHz, CDCl3): δ 152.01 (s), 131.64 (d,J = 2.7 Hz), 127.16
(s), 126.76 (s), 126.24 (s), 125.92 (s), 125.90 (d, J = 3.7 Hz), 125.46 (s),
125.41 (d, J = 9.0 Hz), 124.84 (s), 124.47 (d, J = 8.8 Hz), 124.43 (s),
121.11 (s), 120.77 (s), 109.65 (s), 68.99 (s), 29.44 (s).
HRMS (ESI) calculated for C18H15BrO [M]: 326.0306 found 326.0375。
(2) 1-(ethyoxyl is synthesized) pyrenyl benzimidazole:
In 250 mL dry round-bottomed flask, the benzimidazole of 0.376 g is added, the acetonitrile solution of 100 mL flows back 1 hour,
0.14 g potassium hydroxide, 30 min of reflux are added, the 1-(2- bromine oxethyl of 0.652 g is added) pyrene, 90 DEG C are flowed back 24 hours.
After reaction solution is cooled to room temperature, 10 mL pentanes are added, filtering is washed three times with 20 mL pentanes, and vacuum drying obtains light
Yellow solid 1-(ethyoxyl) pyrenyl benzimidazole (0.617 g, yield 85%).
1H NMR (400 MHz, DMSO) δ 8.53 (s, 1H), 8.19 (m, 4H), 8.01 (ddd, J =
26.1, 18.6, 9.2 Hz, 4H), 7.86 (d, J = 8.1 Hz, 1H), 7.70 (dd, J = 21.8, 8.3
Hz, 2H), 7.33 (t, J = 7.2 Hz, 1H), 7.23 (m, 1H), 4.93 (t, J = 4.9 Hz, 2H),
4.71 (t, J = 5.0 Hz, 2H).
13C NMR (101 MHz, DMSO) δ 144.68 (s), 143.41 (s), 133.99 (s), 131.03 (d,J = 17.3 Hz), 127.20 (s), 126.40 (d, J = 7.2 Hz), 125.88 (s), 124.87 (s),
124.45 (s), 124.24 (s), 123.95 (s), 122.29 (s), 121.52 (s), 120.67 (s),
119.43 (s), 110.66 (s), 109.71 (s), 67.25 (s), 43.87 (s), 39.90 (s), 39.69
(s), 39.49 (s), 39.28 (s), 39.07 (s).
HRMS (ESI) calculated for C25H19N2O [M]: 363.1497; found 363.1508。
(3) 1-(ethyoxyl is synthesized) pyrene -3- benzyl benzimidazole bromide:
In 25 mL Schlenk reaction tubes, under nitrogen protection, by the 1-(ethyoxyl of 0.724 g) pyrenyl benzimidazole is dissolved in
In the acetonitrile of 2 mL, the benzyl bromide of 2.2 mmol is added, 90 DEG C are flowed back 24 hours.Reaction solution is cooled to room temperature, and 6 mL are being added just
Pentane, filtering, 20mL pentane wash three times, and vacuum drying obtains white gray solid 1-(ethyoxyl) pyrene -3- benzyl benzo miaow
Azoles bromide (1.010 g, yield 95%).
1H NMR (400 MHz, DMSO) δ 10.47 (s, 1H), 8.39 (d, J = 8.3 Hz, 1H),
8.23 (m, 4H), 8.04 (ddd, J = 25.5, 13.4, 6.6 Hz, 5H), 7.73 (m, 3H), 7.56 (m,
2H), 7.29 (m, 3H), 5.90 (s, 2H), 5.29 (t, J = 4.2 Hz, 2H), 4.90 (t, J = 4.3
Hz, 2H).
13C NMR (101 MHz, DMSO) δ 152.02 (s), 143.62 (s), 134.37 (s), 131.98 (s),
131.43 (m), 129.27 (d, J = 19.6 Hz), 128.84 (s), 127.68 (s), 127.28 (s),
127.00 (s), 126.33 (s), 125.54 (s), 125.35 (m), 125.18 (d, J = 21.4 Hz),
124.85 (s), 124.42 (s), 121.18 (s), 119.67 (s), 114.77 (s), 114.48 (s),
110.33 (s), 66.73 (s), 50.39 (s), 47.25 (s).
HRMS (ESI) calculated for C32H24N2O+ [M-Br] 452.1883 found: 452.1899。
(4) the benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label is synthesized:
In 25 mL Schlenk reaction tubes, under nitrogen protection, 1-(ethyoxyl is sequentially added) pyrene -3- benzyl benzimidazole
Pyridine is added in bromide (0.55 mmol), potassium carbonate (5 mmol), potassium bromide (10 mmol), palladium chloride (II) (0.5 mmol)
(3 mL) is stirred to react mixture 24 hours at 90 DEG C, after the completion of reaction, solution is cooled to room temperature, passes through short layer diatom
Soil filtering is added the washing of 20 mL methylene chloride, filtrate is concentrated.Solution is slowly added in the hexane of 40 mL, stirs 3h, herein
In the process, yellow substance is generated, is then filtered, the benzimidazole N-heterocyclic carbine palladium metal for obtaining light yellow solid pyrene label is matched
It closes object (0.410 g, yield 88%).
The monocrystalline that the benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label is turned out by solvent diffusion method, through X
Ray single crystal diffraction, proton magnetic and carbon nuclear-magnetism, high resolution mass spectrum have determined its fine structure (referring to Fig. 1 ~ 3).It is further purple
Outer visible spectrum, fluorescence spectrum confirm that the side chain of catalyst contains pyrenyl group (referring to fig. 4 ~ 5).
1H NMR (400 MHz, DMSO) δ 8.96 (d, J = 4.8 Hz, 1H), 8.19 (m, 4H), 8.01
(m, 6H), 7.84 (d, J = 8.6 Hz, 1H), 7.58 (m, 5H), 7.23 (ddd, J = 68.1, 25.4,
12.3 Hz, 6H), 6.13 (d, J = 57.3 Hz, 2H), 5.57 (s, 2H), 5.21 (d, J = 86.1 Hz,
2H).
13C NMR (101 MHz, DMSO) δ 152.65 (s), 136.06 (d, J = 1.2 Hz), 131.63 (s),
131.40 (s), 129.00 (s), 128.58 (d, J = 21.1 Hz), 127.70 (s), 127.10 (m),
126.93 (s), 126.53 (d, J = 21.8 Hz), 125.43 (dd, J = 14.0, 11.9 Hz),124.95
(s), 124.69 (s), 124.47 (s), 123.81 (s), 121.37 (d, J = 1.8 Hz), 119.70 (s),
112.48 (s), 112.03 (s), 110.26 (s), 52.80 (s), 47.92 (s).
HRMS (ESI) calcd. for C37H29N3OPd[M-2Br]: 637.1345 found: 637.1399。
The preparation method of the benzimidazole N-heterocyclic carbine porpezite metal complex of 2 pyrene of embodiment label, including following step
It is rapid:
(1) 1-(2- bromine oxethyl is synthesized) pyrene:
In 100mL dry round-bottomed flask, the acetone of 50 mL is sequentially added, 1- hydroxyl pyrene (2.18g, 10 mmol),
Cs2CO3(4.884g, 15.0 mmol) and 1,2- Bromofume (6.573g, 35.0mmol), 70 DEG C of heating reactions flow back 4 hours.
It is cooled to room temperature to reaction solution, adds methylene chloride and repeatedly extracted with water.Anhydrous MgSO is added in organic phase4Dry, filtering, rotation
It steams.It finally uses column chromatography method and separating-purifying (eluent: petroleum ether: methylene chloride=4:1) is carried out to product, finally obtain
Yellow solid 1-(2- bromine oxethyl) pyrene (1.98g, yield 60%).
(2) 1-(ethyoxyl is synthesized) pyrenyl benzimidazole:
In 250mL dry round-bottomed flask, the benzimidazole of 1.3 mmol is added, the acetonitrile solution of 120mL flows back 1 hour,
1.1 mmol potassium hydroxide reflux 30min is added, the 1-(2- bromine oxethyl of 0.326g is added) pyrene, 80 DEG C of back flow reactions 20 are small
When.After reaction solution is cooled to room temperature, 15mL pentane is added, filtering is washed three times with 30mL pentane, and vacuum drying obtains light
Yellow solid 1-(ethyoxyl) pyrenyl benzimidazole (0.254 g, yield 70%).
(3) 1-(ethyoxyl is synthesized) pyrene -3- benzyl benzimidazole bromide:
In 25 mL Schlenk reaction tubes, under nitrogen protection, by the 1-(ethyoxyl of 0.363 g) pyrenyl benzimidazole is dissolved in
In the acetonitrile of 2 mL, be added 1.0 mmol benzyl bromide, 80 DEG C back flow reaction 20 hours.Reaction solution is cooled to room temperature, and is added 4
ML pentane, filtering, 25 mL pentanes wash three times, and vacuum drying obtains white gray solid 1-(ethyoxyl) pyrene -3- benzyl
Benzimidazole bromide (0.425 g, yield 80%).
(4) the benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label is synthesized:
In 25 mL Schlenk reaction tubes, under nitrogen protection, 1-(ethyoxyl is sequentially added) pyrene -3- benzyl benzimidazole
Pyridine (6 is added in bromide (1.0 mmol), potassium carbonate (3 mmol), potassium bromide (8 mmol), palladium chloride (II) (1 mmol)
ML), mixture is stirred to react 20 hours at 80 DEG C, after the completion of reaction, solution is cooled to room temperature, passes through short layer diatomite mistake
Filter is added the washing of 30 mL methylene chloride, filtrate is concentrated.Solution is slowly added in the hexane of 50 mL, 3h is stirred, in this process
In, yellow substance is generated, is then filtered, the benzimidazole N-heterocyclic carbine porpezite metal complex of light yellow solid pyrene label is obtained
(0.635 g, yield 79%).
The preparation method of the benzimidazole N-heterocyclic carbine porpezite metal complex of 3 pyrene of embodiment label, including following step
It is rapid:
(1) 1-(2- bromine oxethyl is synthesized) pyrene:
In 100mL dry round-bottomed flask, the acetone of 60mL, 1- hydroxyl pyrene (2.18g, 10 mmol), Cs are sequentially added2CO3
(8.145g, 25.0 mmol) and 1,2- Bromofume (8.451g, 45.0mmol), 80 DEG C of heating are reacted 15 hours.To reaction solution
It is cooled to room temperature, adds methylene chloride and repeatedly extracted with water.Anhydrous MgSO is added in organic phase4Dry, filtering, revolving.Finally use
Column chromatography for separation method carries out separating-purifying (eluent: petroleum ether: methylene chloride=4:1) to product, finally obtains yellow solid 1-
(2- bromine oxethyl) pyrene (1.5 g, yield 46%).
(2) 1-(ethyoxyl is synthesized) pyrenyl benzimidazole:
In 250mL dry round-bottomed flask, the benzimidazole of 2.0 mmol is added, the acetonitrile solution of 150mL flows back 1 hour,
1.5 mmol potassium hydroxide reflux 30min is added, the 1-(2- bromine oxethyl of 1.0 mmol is added) pyrene, 100 DEG C of back flow reactions
30 hours.After reaction solution is cooled to room temperature, 20mL pentane is added, filtering is washed three times with 60mL pentane, is dried in vacuo
To faint yellow solid 1-(ethyoxyl) pyrenyl benzimidazole (0.261 g, yield 72%).
(3) 1-(ethyoxyl is synthesized) pyrene -3- benzyl benzimidazole bromide:
In 25 mL Schlenk reaction tubes, under nitrogen protection, by the 1-(ethyoxyl of 1.0 mmol) pyrenyl benzimidazole is molten
In the acetonitrile of 4 mL, be added 1.5 mmol benzyl bromide, 100 DEG C back flow reaction 30 hours.Reaction solution is cooled to room temperature, and is added
10 mL pentanes, filtering, 40 mL pentanes wash three times, and vacuum drying obtains white gray solid 1-(ethyoxyl) pyrene -3- benzyl
Base benzimidazole bromide (0.399 g, yield 75%).
(4) the benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label is synthesized:
In 25 mL Schlenk reaction tubes, under nitrogen protection, 1-(ethyoxyl is sequentially added) pyrene -3- benzyl benzimidazole
Pyridine (3 is added in bromide (1.5 mmol), potassium carbonate (6 mmol), potassium bromide (12 mmol), palladium chloride (II) (1.0 mmol)
ML), mixture is stirred to react 30 hours at 100 DEG C, after the completion of reaction, solution is cooled to room temperature, passes through short layer diatomite
Filtering is added the washing of 10 mL methylene chloride, filtrate is concentrated.Solution is slowly added in the hexane of 10 mL, stirs 3h, herein mistake
Cheng Zhong generates yellow substance, then filters, and obtains the benzimidazole N-heterocyclic carbine palladium metal cooperation of light yellow solid pyrene label
Object (0.502 g, yield 63%).
The benzimidazole N-heterocyclic carbine porpezite metal complex of the resulting pyrene of above-described embodiment 1 ~ 3 label is answered as catalyst
For in iodo aromatic hydrocarbon, carbon monoxide (CO), three component Sonogashira carbonylation of terminal alkyne.
Embodiment 4
Volume be 50 mL autoclave in be added, be added 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol phenylacetylene,
2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).Confined reaction
Kettle is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, is controlled by temperature controller
Temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent 6890/
5973 gas chromatograph-mass spectrometers carry out qualitative analysis, target product 1, and 3- diphenyl -2- propine -1- ketone is selectively greater than 99%, and separation is received
Rate 98%.
1H NMR (400 MHz, CDCl3) δ 8.15 (m, 2H), 7.57 (m, 3H), 7.39 (m, 5H)。
13C NMR (100MHz, CDCl3) δ 178.05 (s), 136.91 (s), 134.16 (s), 133.10
(s), 130.84 (s), 129.61 (s), 128.69 (d, J = 6.2 Hz), 120.15 (s), 93.15 (s),
86.92 (s)。
HRMS (ESI) calcd. for C15H11O [M+H]: 207.0804, found: 207.0804。
IR (KBr, cm−1) 2203, 1644, 1254, 1002, 755。
Embodiment 5
It is to be added in 50 mL autoclaves in volume, 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol phenylacetylenes, 2.0 is added
Mmol potassium carbonate, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).Closed reactor,
Reaction kettle is replaced 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, controls temperature by temperature controller
100 DEG C are slowly increased to, is reacted 18 hours, is cooled to room temperature, unloads kettle, resulting liquid Agilent 6890/5973 will be reacted
Gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1, and 3- diphenyl -2- propine -1- ketone is selectively greater than 99%, separation yield
15%。
Embodiment 6
Volume be 50 mL autoclave in be added, be added 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol phenylacetylenes,
2.0 mmol sodium carbonate, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).Confined reaction
Kettle is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, is controlled by temperature controller
Temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent 6890/
5973 gas chromatograph-mass spectrometers carry out qualitative analysis, target product 1, and 3- diphenyl -2- propine -1- ketone is selectively greater than 99%, and separation is received
Rate 10%.
Embodiment 7
It is added in the autoclave that volume is 50 mL, the benzene second of 5 mL toluene, the iodobenzene of 1 mmol, 1.2 mmol is added
Alkynes, the sodium acetate of 2.0 mmol, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).
Closed reactor is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by controlling
Warm instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid and use
6890/5973 gas chromatograph-mass spectrometer of Agilent carries out qualitative analysis, target product 1,3- diphenyl -2- propine -1- ketone selectivity
Greater than 99%, separation yield 25%.
Embodiment 8
It is added in the autoclave that volume is 50 mL, the benzene of 5 mL tetrahydrofurans, 1 mmol iodobenzene, 1.2 mmol is added
Acetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is close
Reaction kettle is closed, is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature control
Instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1, and 3- diphenyl -2- propine -1- ketone is selectively greater than 99%,
Separation yield 90%.
Embodiment 9
It is added in the autoclave that volume is 50 mL, 5 mL dioxane, 1 mmol iodobenzene, 1.2 mmol benzene second is added
Alkynes, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is closed
Reaction kettle is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature controller
Control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1, and 3- diphenyl -2- propine -1- ketone is selectively greater than 99%,
Separation yield 88%.
Embodiment 10
Be to be added in 50 mL autoclaves in volume, be added the acetonitrile of 5 mL, 1 mmol iodobenzene, 1.2 mmol phenylacetylenes,
The benzimidazole N-heterocyclic carbine porpezite metal complex of 2.0 mmol triethylamines, 0.5 mol% (relative to iodobenzene).It is closed anti-
Kettle is answered, is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature control instrument control
Temperature processed is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1, and 3- diphenyl -2- propine -1- ketone is selectively greater than 99%,
Separation yield 82%.
Embodiment 11
Volume be 50 mL autoclave in be added, be added 5 mL methyl phenyl ethers anisoles, 1 mmol iodobenzene, 1.2 mmol phenylacetylenes,
2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).Confined reaction
Kettle is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, is controlled by temperature controller
Temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent 6890/
5973 gas chromatograph-mass spectrometers carry out qualitative analysis, target product 1, and 3- diphenyl -2- propine -1- ketone is selectively greater than 99%, and separation is received
Rate 67%.
Embodiment 12
It is to be added in 50 mL autoclaves in volume, 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol phenylacetylenes, 2.0 is added
Mmol triethylamine, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).Closed reactor,
Reaction kettle is replaced 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, controls temperature by temperature controller
80 DEG C are slowly increased to, is reacted 18 hours, is cooled to room temperature, unloads kettle, resulting liquid Agilent 6890/5973 will be reacted
Gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1, and 3- diphenyl -2- propine -1- ketone is selectively greater than 99%, separation yield
83%。
Embodiment 13
Volume be 50 mL autoclave in be added, be added 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol phenylacetylenes,
The benzimidazole N-heterocyclic carbine porpezite metal complex of 2.0 mmol triethylamines, 0.5 mol% (relative to iodobenzene).It is closed anti-
Kettle is answered, is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 1.0 MPa, by temperature control instrument control
Temperature processed is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1, and 3- diphenyl -2- propine -1- ketone is selectively greater than 99%,
Separation yield 82%.
Embodiment 14
Volume be 50 mL autoclave in be added, be added 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol phenylacetylenes,
2.0 mmol triethylamines, 0.25 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is closed anti-
Kettle is answered, is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature control instrument control
Temperature processed is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1, and 3- diphenyl -2- propine -1- ketone is selectively greater than 99%,
Separation yield 92%.
Embodiment 15
Volume be 50 mL autoclave in be added, be added 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol phenylacetylenes,
2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).Confined reaction
Kettle is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, is controlled by temperature controller
Temperature is slowly increased to 100 DEG C, reacts 4 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent 6890/
5973 gas chromatograph-mass spectrometers carry out qualitative analysis, target product 1, and 3- diphenyl -2- propine -1- ketone is selectively greater than 99%, and separation is received
Rate 55%.
Embodiment 16
Volume be 50 mL autoclave in be added, be added 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol phenylacetylenes,
2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).Confined reaction
Kettle is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, is controlled by temperature controller
Temperature is slowly increased to 100 DEG C, reacts 6 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent 6890/
5973 gas chromatograph-mass spectrometers carry out qualitative analysis, target product 1, and 3- diphenyl -2- propine -1- ketone is selectively greater than 99%, and separation is received
Rate 85%.
Embodiment 17
Volume be 50 mL autoclave in be added, be added 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol phenylacetylenes,
2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).Confined reaction
Kettle is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, is controlled by temperature controller
Temperature is slowly increased to 100 DEG C, reacts 12 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent 6890/
5973 gas chromatograph-mass spectrometers carry out qualitative analysis, target product 1, and 3- diphenyl -2- propine -1- ketone is selectively greater than 99%, and separation is received
Rate 95%.
Embodiment 18
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol 2- methyl iodobenzene, 1.2 mmol benzene is added
Acetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is close
Reaction kettle is closed, is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature control
Instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1- (2- tolyl) -3- phenyl -2- propine -1- ketone selectivity
Greater than 99%, separation yield 75%.
1H NMR (400 MHz, CDCl3) δ 8.23 (dd, J = 7.8, 1.2 Hz, 1H), 7.59 (m,
2H), 7.35 (m, 5H), 7.20 (m, 1H), 2.61 (s, 3H)。
13C NMR (100 MHz, CDCl3) δ 179.80 (s), 140.51 (s), 135.76 (s), 133.19
(s), 132.94 (s), 132.19 (s), 130.60 (s), 128.66 (s), 125.90 (s), 120.38 (s),
91.82 (s), 88.40 (s), 21.96 (s)。
HRMS (ESI) calcd. for C16H13O [M+H]: 221.0961, found: 221.0961。
IR (KBr, cm−1) 2934, 2203, 1642, 1321, 1004, 725。
Embodiment 19
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol 3- methyl iodobenzene, 1.2 mmol benzene is added
Acetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is close
Reaction kettle is closed, is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature control
Instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1- (3- tolyl) -3- phenyl -2- propine -1- ketone selectivity
Greater than 99%, separation yield 98%.
1H NMR (400 MHz, CDCl3) δ 8.23 (dd, J = 7.8, 1.2 Hz, 1H), 7.59 (m,
2H), 7.35 (m, 5H), 7.20 (m, 1H), 2.61 (s, 3H)。
13C NMR (100 MHz, CDCl3) δ 179.80 (s), 140.51 (s), 135.76 (s), 133.19
(s), 132.94 (s), 132.19 (s), 130.60 (s), 128.66 (s), 125.90 (s), 120.38 (s),
91.82 (s), 88.40 (s), 21.96 (s)。
HRMS (ESI) calcd. for C16H13O [M+H]: 221.0961, found: 221.0961。
IR (KBr, cm−1) 2934, 2203, 1642, 1321, 1004, 725。
Embodiment 20
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol 4- methyl iodobenzene, 1.2 mmol benzene is added
Acetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is close
Reaction kettle is closed, is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature control
Instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1- (4- tolyl) -3- phenyl -2- propine -1- ketone selectivity
Greater than 99%, separation yield 87%.
1H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.2 Hz, 2H), 7.54 (dd, J = 8.3,
1.4 Hz, 2H), 7.30 (m, 3H), 7.17 (d, J = 8.0 Hz, 2H), 2.30 (s, 3H)。
13C NMR (100 MHz, CDCl3) δ 177.68 (s), 145.28 (s), 134.64 (s), 133.05
(s), 130.74 (s), 129.72 (s), 129.40 (s), 128.71 (s), 120.25 (s), 92.63 (s),
87.04 (s), 21.86 (s)。
HRMS (ESI) calcd. for C16H13O [M+H]: 221.0961, found: 221.0953。
IR (KBr, cm−1) 2913, 2203, 1637, 1288, 1009, 765。
Embodiment 21
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol 4- methoxyl group iodobenzene, 1.2 mmol is added
Phenylacetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).
Closed reactor is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by controlling
Warm instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid and use
6890/5973 gas chromatograph-mass spectrometer of Agilent carries out qualitative analysis, target product 1- (4- methoxyphenyl) -3- phenyl -2- third
Alkynes -1- ketone is selectively greater than 99%, separation yield 70%.
1H NMR (400 MHz, CDCl3) δ 8.20 (d, J = 8.9 Hz, 2H), 7.68 (d, J = 6.8
Hz, 2H), 7.44 (m, 3H), 6.99 (d, J = 8.9 Hz, 2H), 3.90 (s, 3H).
13C NMR (100 MHz, CDCl3) δ 55.6, 86.9, 92.3, 113.9, 120.4, 128.7, 130.3,
130.6,132.0, 133.0, 164.5, 176.7.
HRMS (ESI) calcd.for C17H15O2 [M+H]: 251.1073, found: 251.1076.
IR (KBr, cm−1) 2203, 1630, 1487, 1254, 1004, 750
Embodiment 22
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol 3- methoxyl group iodobenzene, 1.2 mmol is added
Phenylacetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).
Closed reactor is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by controlling
Warm instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid and use
6890/5973 gas chromatograph-mass spectrometer of Agilent carries out qualitative analysis, target product 1- (3- methoxyphenyl) -3- phenyl -2- third
Alkynes -1- ketone, selectivity are greater than 99%, separation yield 85%.
1H NMR (400 MHz, CDCl3) δ 7.76 (m, 1H), 7.58 (m, 3H), 7.33 (tdd, J =
8.5, 6.8, 3.7 Hz, 4H), 7.07 (ddd, J = 8.2, 2.7, 0.9 Hz, 1H), 3.77 (s, 3H)。
13C NMR (101 MHz, CDCl3) δ 176.69 (s), 158.78 (s), 137.22 (s), 132.03
(s), 129.78 (s), 128.62 (s), 127.66 (s), 121.79 (s), 119.88 (s), 119.06 (s),
111.84 (s), 91.94 (s), 85.94 (s), 54.42 (s)。
HRMS (ESI) calcd. for C17H15O2 [M+H]: 251.1073, found: 251.1076。
IR (KBr, cm−1) 2203, 1634, 1521, 1302, 1159, 757。
Embodiment 23
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol 2- methoxyl group iodobenzene, 1.2 mmol is added
Phenylacetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).
Closed reactor is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by controlling
Warm instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid and use
6890/5973 gas chromatograph-mass spectrometer of Agilent carries out qualitative analysis, target product 1- (2- methoxyphenyl) -3- phenyl -2- third
Alkynes -1- ketone is selectively greater than 99%, separation yield 80%.
1H NMR (400 MHz, CDCl3) δ 7.95 (m, 1H), 7.48 (m, 2H), 7.39 (dd, J =
8.3, 7.4 Hz, 1H), 7.26 (m, 3H), 6.89 (m, 2H), 3.80 (d, J = 2.1 Hz, 3H)。
13C NMR (100 MHz, CDCl3) δ 176.70 (s), 159.85 (s), 135.16 (s), 132.96
(s), 132.56 (s), 130.54 (s), 128.66 (s), 126.68 (s), 120.64 (s), 120.35 (s),
112.30 (s), 91.63 (s), 89.31 (s), 55.93 (s)。
HRMS (ESI) calcd. for C17H15O2 [M+Na]: 259.0735, found: 259.0715。
IR (KBr, cm−1) 2203, 1630, 1268, 1016, 757。
Embodiment 24
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol 4- fluorine iodobenzene, 1.2 mmol benzene second is added
Alkynes, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is closed
Reaction kettle is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature controller
Control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1- (4- fluorophenyl) -3- phenyl -2- propine -1- ketone selectivity
Greater than 99%, separation yield 90%.
1H NMR (400 MHz, CDCl3) δ 8.11 (dd, J = 8.9, 5.4 Hz, 2H), 7.54 (dd, J
= 8.3, 1.3 Hz, 2H), 7.31 (m, 3H), 7.05 (m, 2H)。
13C NMR (100 MHz, CDCl3) δ 176.68 (s), 164.51 (s), 132.97 (s), 132.00
(s), 130.58 (s), 130.36 (s), 128.66 (s), 120.40 (s), 113.90 (s), 92.31 (s),
86.95 (s), 55.61 (s)。
HRMS (ESI) calcd. for C15H10FO [M+H]: 225.0710, found: 225.0705。
IR (KBr, cm−1) 2210, 1630, 1222, 1028, 845, 730。
Embodiment 25
It is added in the autoclave that volume is 50 mL, the toluene of 5 mL, 1 mmol 4- chlorine iodobenzene, 1.2 mmol benzene is added
Acetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is close
Reaction kettle is closed, is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature control
Instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1- (4- chlorphenyl) -3- phenyl -2- propine -1- ketone selectivity
Greater than 99%, separation yield 79%.
1H NMR (400 MHz, CDCl3)δ 8.15-8.17 (m, 2H), 7.68-7.70 (m, 3H), 7.42-
7.7.51 (m,5H)。
13C NMR (100 MHz, CDCl3) δ 86.6, 93.6, 12.0, 128.7, 129.0, 130.9,
131.0, 133.1,135.3, 140.7 176.7。
HRMS (ESI) calcd. for C15H10ClO [M+H]: 241.0415, found: 241.0407。
IR (KBr, cm−1) 2203, 1657, 1213, 1002, 743, 675。
Embodiment 26
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol 4- trifluoromethyl iodobenzene, 1.2 mmol is added
Phenylacetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).
Closed reactor is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by controlling
Warm instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid and use
6890/5973 gas chromatograph-mass spectrometer of Agilent carries out qualitative analysis, target product 1- (4- trifluoromethyl) -3- phenyl -2-
Propine -1- ketone is selectively greater than 99%, separation yield 95%.
1H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 8.1 Hz, 2H), 7.77 (d, J = 8.2
Hz, 2H), 7.69 (m, 2H), 7.50 (t, J = 7.4 Hz, 1H), 7.43 (m, 2H)。
13C NMR (100 MHz, CDCl3) δ 176.66 (s), 139.40 (s), 133.21 (s), 131.21
(s), 129.80 (s), 128.80 (s), 125.70 (d, J = 3.7 Hz), 119.68 (s), 94.47 (s),
86.60 (s)。
Embodiment 27
Volume be 50 mL autoclave in be added, be added 5 mL toluene, 1 mmol 1- iodo naphthalene, 1.2 mmol phenylacetylenes,
2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).Confined reaction
Kettle is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, is controlled by temperature controller
Temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent 6890/
5973 gas chromatograph-mass spectrometers carry out qualitative analysis, target product 1- (1- naphthalene) -3- phenyl -2- propine -1- ketone is selectively greater than
99%, separation yield 92%.
1H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 8.1 Hz, 2H), 7.77 (d, J = 8.2
Hz, 2H), 7.69 (m, 2H), 7.50 (t, J = 7.4 Hz, 1H), 7.43 (m, 2H)。
13C NMR (100 MHz, CDCl3) δ 176.66 (s), 139.40 (s), 133.21 (s), 131.21
(s), 129.80 (s), 128.80 (s), 125.70 (d, J = 3.7 Hz), 119.68 (s), 94.47 (s),
86.60 (s)。
Embodiment 28
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol 4- iodo-benzoic acid methyl esters, 1.2 mmol is added
Phenylacetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).
Closed reactor is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by controlling
Warm instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid and use
6890/5973 gas chromatograph-mass spectrometer of Agilent carries out qualitative analysis, target product 1- (4- methyl formate phenyl) -3- phenyl -2-
Propine -1- ketone is selectively greater than 99%, separation yield 66%.
1H NMR (400 MHz, CDCl3) δ 8.19 (m, 2H), 8.10 (m, 2H), 7.62 (dd, J =
5.2, 3.3 Hz, 2H), 7.38 (m, 3H), 3.88 (d, J = 4.0 Hz, 3H)。
13C NMR (100 MHz, CDCl3)δ 176.17 (s), 165.10 (s), 138.89 (s), 133.66
(s), 132.16 (s), 130.08 (s), 128.79 (s), 128.38 (s), 127.75 (s), 118.78 (s),
93.17 (s), 85.79 (s), 51.52 (s)。
IR (KBr, cm−1) 2210, 1734, 1637, 1281, 1111, 702
Embodiment 29
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol 4- fluorophenethyls is added
Alkynes, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is closed
Reaction kettle is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature controller
Control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1- phenyl -3- (4- fluorophenyl) -2- propine -1- ketone selectivity
Greater than 99%, separation yield 88%.
1H NMR (400 MHz, CDCl3) δ 8.21 (m, 2H), 7.69 (m, 3H), 7.53 (t, J = 7.6
Hz, 2H), 7.13 (t, J = 8.7 Hz, 2H)。
13C NMR (100 MHz, CDCl3) δ 177.90 (s), 165.31 (s), 162.79 (s), 136.84
(s), 135.37 (d, J = 9.0 Hz), 134.19 (s), 129.56 (s), 128.67 (s), 116.38 (s),
116.16 (s), 91.98 (s), 86.83 (s)。
HRMS (ESI) calcd.for C15H10FO, 225.0710; found 225.0716。
IR (KBr, cm−1) 2199, 1648, 1259, 1012, 775。
Embodiment 30
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol 4- bromobenzene second is added
Alkynes, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is closed
Reaction kettle is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature controller
Control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1- phenyl -3- (4- bromophenyl) -2- propine -1- ketone selectivity
Greater than 99%, separation yield 65%.
1H NMR (400 MHz, CDCl3) δ 8.13 (dd, J = 8.3, 1.2 Hz, 2H), 7.56 (m,
1H), 7.47 (m, 6H)。
13C NMR (100 MHz, CDCl3) δ 177.82 (s), 136.74 (s), 134.32 (d, J = 6.8
Hz), 132.13 (s), 130.59 (s), 129.60 (s), 125.62 (s), 119.08 (s), 91.65 (s),
87.70 (s)。
HRMS (ESI) calculated for C15H9BrO[M+H]+, 284.9915; found284.9918。
IR (KBr, cm−1) 2208, 1654, 1254, 1012, 775。
Embodiment 31
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol 4- methylbenzene second is added
Alkynes, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is closed
Reaction kettle is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature controller
Control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1- phenyl -3- (4- tolyl) -2- propine -1- ketone selectivity
Greater than 99%, separation yield 98%.
1H NMR (400 MHz, CDCl3) δ 8.12 (dd, J = 8.3, 1.3 Hz, 2H), 7.46 (m,
5H), 7.11 (d, J = 8.0 Hz, 2H), 2.28 (s, 3H)。
13C NMR (100 MHz, CDCl3) δ 176.99 (s), 140.53 (s), 135.92 (s), 132.97
(s), 132.07 (s), 128.47 (d, J = 3.0 Hz), 127.55 (s), 115.93 (s), 92.79 (s),
85.75 (s), 76.37 (s), 76.05 (s), 75.73 (s), 20.71 (s)。
HRMS (ESI) calcd. for C16H13O [M+H]+: 221.0961, found: 221.0953。
IR (KBr, cm−1) 2203, 1637, 1275, 1008, 811, 702。
Embodiment 32
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol 4- ethylo benzene second is added
Alkynes, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is closed
Reaction kettle is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature controller
Control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, target product 1- phenyl -3- (4- ethylbenzene) -2- propine -1- ketone selectivity
Greater than 99%, separation yield 85%.
1H NMR (400 MHz, CDCl3) δ 8.23 (m, 2H), 7.62 (dd, J = 11.6, 4.6 Hz,
3H), 7.52 (t, J = 7.6 Hz, 2H), 7.26 (m, 2H), 2.70 (q, J = 7.6 Hz, 2H), 1.26
(t, J = 7.6 Hz, 3H)。
13C NMR (101 MHz, CDCl3) δ 178.10 (s), 147.78 (s), 137.04 (s), 134.00
(s), 133.26 (s), 129.57 (s), 128.60 (s), 128.33 (s), 117.27 (s), 93.86 (s),
86.78 (s), 29.06 (s), 15.18 (s)。
HRMS (ESI) calculated for C17H15O[M+H]+:235.1117; found 235.1112。
IR (KBr, cm−1) 2194, 1630, 1209, 1171, 1007, 696。
Embodiment 33
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol 4- n-butylbenzenes is added
Acetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is close
Reaction kettle is closed, is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature control
Instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, the choosing of target product 1- phenyl -3- (4- n-butylphenyl) -2- propine -1- ketone
Selecting property is greater than 99%, separation yield 97%.
1H NMR (400 MHz, CDCl3) δ 8.09 (m, 2H), 7.42 (dd, J = 34.5, 7.9 Hz,
5H), 7.08 (d, J = 8.2 Hz, 2H), 2.49 (m, 2H), 1.46 (dd, J = 8.6, 6.8 Hz, 2H),
1.21 (dd, J = 15.0, 7.4 Hz, 2H), 0.79 (d, J = 7.4 Hz, 3H)。
13C NMR (100 MHz, CDCl3) δ 178.00 (s), 146.54 (s), 137.03 (s), 134.04
(s), 133.20 (s), 129.55 (s), 128.89 (s), 128.63 (s), 117.20 (s), 93.91 (s),
86.86 (s), 77.53 (s), 77.21 (s), 76.90 (s), 35.80 (s), 33.24 (s), 22.34 (s),
13.95 (s)。
HRMS (ESI) calcd. for C19H19O [M+H]+: 263.1430, found: 263.1440。
IR (KBr, cm−1 ) 2926, 2203, 1644, 1288, 1009, 695。
Embodiment 34
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol 4- tert-butyl benzenes is added
Acetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is close
Reaction kettle is closed, is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature control
Instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, the choosing of target product 1- phenyl -3- (4- tert-butyl-phenyl) -2- propine -1- ketone
Selecting property is greater than 99%, separation yield 90%.
1H NMR (400 MHz, CDCl3) δ 8.23 (dd, J = 8.3, 1.2 Hz, 2H), 7.61 (t, J =
8.5 Hz, 3H), 7.50 (t, J = 7.6 Hz, 2H), 7.43 (d, J = 8.5 Hz, 2H), 1.33 (s,
9H)。
13C NMR (100 MHz, CDCl3) δ 178.07 (s), 154.61 (s), 137.05 (s), 134.03
(s), 133.03 (s), 129.57 (s), 128.63 (s), 125.79 (s), 117.07 (s), 93.82 (s),
86.80 (s), 35.12 (s), 31.08 (s)。
HRMS (ESI) calculated for C19H19O[M+H]+:263.1430; found 263.1435。
IR (KBr, cm−1)2195, 1650, 1597, 1509, 1298, 839, 705。
Embodiment 35
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol 4- methoxybenzenes is added
Acetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).It is close
Reaction kettle is closed, is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by temperature control
Instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid Agilent
6890/5973 gas chromatograph-mass spectrometer carries out qualitative analysis, the choosing of target product 1- phenyl -3- (4- methoxyphenyl) -2- propine -1- ketone
Selecting property is greater than 99%, separation yield 95%.
1H NMR (400 MHz, CDCl3) δ 8.12 (m, 2H), 7.49 (m, 5H), 6.84 (m, 2H),
3.75 (s, 3H)。
13C NMR (100 MHz, CDCl3) δ 178.05 (s), 161.77 (s), 137.07 (s), 135.18
(s), 133.94 (s), 129.50 (s), 128.59 (s), 114.46 (s), 111.89 (s), 94.37 (s),
86.91 (s), 77.41 (s), 77.10 (s), 76.78 (s), 55.46 (s)。
HRMS (ESI) calcd. for C16H13O2 [M+H]+: 237.0910, found: 237.0906。
IR (KBr, cm−1 ) 2920, 2203, 1657, 1288, 1002, 839, 689。
Embodiment 36
It is added in the autoclave that volume is 50 mL, 5 mL toluene, 1 mmol iodobenzene, 1.2 mmol 4- n-pentyloxies is added
Phenylacetylene, 2.0 mmol triethylamines, 0.5 mol% benzimidazole N-heterocyclic carbine porpezite metal complex (relative to iodobenzene).
Closed reactor is replaced reaction kettle 3 times with carbon monoxide, closed reactor.Being filled with CO gas pressure is 2.0 MPa, by controlling
Warm instrument control temperature is slowly increased to 100 DEG C, reacts 18 hours, is cooled to room temperature, unloads kettle, will react resulting liquid and use
6890/5973 gas chromatograph-mass spectrometer of Agilent carries out qualitative analysis, target product 1- phenyl -3- (4- n-pentyloxy phenyl) -2-
Propine -1- ketone is selectively greater than 99%, separation yield 90%.
1H NMR (400 MHz, CDCl3) δ 8.13 (m, 2H), 7.53 (m, 3H), 7.43 (d, J = 7.8
Hz, 2H), 6.82 (d, J = 8.8 Hz, 2H), 3.89 (t, J = 6.6 Hz, 2H), 1.71 (m, 2H),
1.32 (dd, J = 7.8, 4.7 Hz, 4H), 0.85 (t, J = 7.1 Hz, 3H)。
13C NMR (100 MHz, CDCl3) δ 178.04 (s), 161.42 (s), 137.11 (s), 135.18
(s), 133.89 (s), 129.49 (s), 128.57 (s), 114.92 (s), 111.58 (s), 94.58 (s),
86.92 (s), 68.27 (s), 28.80 (s), 28.14 (s), 22.44 (s), 14.02 (s)。
HRMS (ESI) calcd.for C20H21O2[M+H]: 293.1542; found 293.1549。
IR (KBr, cm−1) 2208, 1634, 1254, 1012, 785。
Claims (3)
1. the benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label, it is characterised in that: using benzimidazole as skeleton, with pyrrole
Pyridine is the benzimidazole N-heterocyclic carbine porpezite metal complex of the label of pyrene prepared by axial ligand, structural formula are as follows:
。
2. the preparation method of the benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label as described in claim 1, including
Following steps:
(1) 1-(2- bromine oxethyl is synthesized) pyrene:
Using acetone as solvent, by 1- hydroxyl pyrene, cesium carbonate, 1,2- Bromofume 1:1.5 ~ 2.5:3.5 ~ 4.5 in molar ratio, in 60
~ 80 DEG C of heating reactions flow back 4 ~ 15 hours, isolate and purify product after reaction to get 1-(2- bromine oxethyl) pyrene；
(2) 1-(ethyoxyl is synthesized) pyrenyl benzimidazole:
Using acetonitrile as reaction dissolvent, by the 1-(2- bromine oxethyl) pyrene, benzimidazole, potassium hydroxide in molar ratio 1:1.3 ~
2.0:1.1 ~ 1.5 flow back 20 ~ 30 hours in 80 ~ 100 DEG C of heating reactions, isolate and purify product after reaction to get 1-(second
Oxygroup) pyrenyl benzimidazole；
(3) 1-(ethyoxyl is synthesized) pyrene -3- benzyl benzimidazole bromide:
Using acetonitrile as reaction dissolvent, under inert atmosphere, by the 1-(ethyoxyl) pyrenyl benzimidazole, benzyl bromide in molar ratio 1:
1.0 ~ 1.5, it flows back 20 ~ 30 hours in 80 ~ 100 DEG C of heating reactions.Isolate and purify product after reaction to get 1-(ethyoxyl)
Pyrene -3- benzyl benzimidazole bromide；
(4) the benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label is synthesized:
Using pyridine as reaction dissolvent, under inert atmosphere, by palladium chloride, the 1-(ethyoxyl) pyrene -3- benzyl benzimidazole bromine
Salt, potassium carbonate, potassium bromide 1:1.0 ~ 1.5:3 ~ 10:8 ~ 20 in molar ratio, are heated to reflux 20 ~ 30 hours, anti-in 80 ~ 100 DEG C
After answering, the benzimidazole N-heterocyclic carbine porpezite metal complex that product marks to get pyrene is isolated and purified after reaction.
3. the application of the benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label as described in claim 1, feature exist
In: the benzimidazole N-heterocyclic carbine porpezite metal complex of pyrene label is as catalyst in iodo aromatic hydrocarbon, carbon monoxide, end
In three component Sonogashira carbonylation of alkynes, one-step synthesis intermediate α, β-unsaturation acetylenic ketone；The benzimidazole nitrogen
The additional amount of heterocycle carbine porpezite metal complex be the iodo aromatic hydrocarbon mole 0.5 ~ 3 mol%, preferably 0.1 ~
0.25mol%。
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| CN112275322A (en) * | 2020-11-03 | 2021-01-29 | 中国科学院兰州化学物理研究所 | Preparation method and application of supported CNTs @ NHC-Cu catalytic material |
| WO2022081953A1 (en) * | 2020-10-15 | 2022-04-21 | Saudi Arabian Oil Company | Synthesis of alkynones via carbonylative sonogashira coupling reactions catalyzed by pd(ii)-n-heterocyclic carbene-pyridine complexes |
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| CN104607248A (en) * | 2015-01-23 | 2015-05-13 | 齐鲁工业大学 | Pyrene-4,5,9,10-quadri-imine-(arylamine) palladium chloride and application thereof in Heck reaction |
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| CHUNYAN ZHANG ET AL.: "Aryl-palladium-NHC complex: efficient phosphine-free catalyst precursors for the carbonylation of aryl iodides with amines or alkynes", 《ORG. BIOMOL. CHEM.》 * |
| MANSUR IBRAHIM ET AL.: "Novel (N‐heterocyclic carbene)Pd(pyridine)Br2 complexes for carbonylative Sonogashira coupling reactions: Catalytic efficiency and scope for arylalkynes, alkylalkynes and dialkynes", 《APPL ORGANOMETAL CHEM.》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022081953A1 (en) * | 2020-10-15 | 2022-04-21 | Saudi Arabian Oil Company | Synthesis of alkynones via carbonylative sonogashira coupling reactions catalyzed by pd(ii)-n-heterocyclic carbene-pyridine complexes |
| US11691135B2 (en) | 2020-10-15 | 2023-07-04 | King Fahd University Of Petroleum & Minerals | Synthesis of alkynones via carbonylative Sonogashira coupling reactions catalyzed by Pd(II)-N-Heterocyclic carbene-pyridine complexes |
| CN112275322A (en) * | 2020-11-03 | 2021-01-29 | 中国科学院兰州化学物理研究所 | Preparation method and application of supported CNTs @ NHC-Cu catalytic material |
| CN112275322B (en) * | 2020-11-03 | 2022-01-25 | 中国科学院兰州化学物理研究所 | Preparation method and application of supported CNTs @ NHC-Cu catalytic material |
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