CN102503748B - Copper catalyst system for sonogashira coupling reaction - Google Patents
Copper catalyst system for sonogashira coupling reaction Download PDFInfo
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Abstract
The invention discloses a copper catalyst system for sonogashira coupling reaction. The copper catalyst system comprises copper salt, phosphine ligands and inorganic alkaline according to a mol ratio of 1: (50000-200000): (200000-1000000), wherein the copper salt is selected from one kind of materials or a mixture of more than one kind of materials from copper iodide, copper acetylacetonate, copper bromide, copper sulfate and copper powder, and the phosphine ligands are trivalent phosphine ligands. The invention discloses the novel copper catalyst system for sonogashira coupling reaction. Compared with the existing noble-metal-containing catalyst system, the catalyst system has the advantages that the cheap copper salt is used for replacing the noble metal, the cost is greatly reduced, inaddition, the environmental-friendly water can be adopted as reaction solvents, the environment is favorably protected, the cost is favorably saved, and the reaction also obtains great progress in green chemistry.
Description
Technical field
The invention belongs to catalyst field, be specifically related to the copper catalyst system of Yuan coupled reaction of a kind of Yong Yu, this catalyst system can a Cuiization Yuan coupled reaction prepare acetylene compound in water.
Background technology
Terminal alkyne and sp by the catalysis of Pd/Cu mixed catalyst
2Cross-coupling reaction between the halogenide of type carbon (aryl halide) is Yuan coupled reaction of Bei Cheng Zhi Wei (Sonogashira coupling reaction is called for short the Sonogashira reaction) usually.This reaction as far back as 1975 by Heck, Cassar and Sonogashira etc. are independent to find that through nearly 30 years development, it is known by people gradually, and becomes an important name reaction.At present, Sonogashira is reflected in synthesizing of replacement alkynes and big conjugation alkynes and has obtained using widely, and effective, the most direct method that is considered to synthetic acetylene hydrocarbon compound, thereby at a lot of natural compoundss, obtained widespread use in the agricultural chemicals medicine, brand-new material and nano molecular device synthetic.
Traditional catalyzer that is used for the Sonogashira linked reaction is palladium complex normally, is aided with cuprous iodide simultaneously as co-catalyst in the presence of phosphorus-containing ligand, and employed solvent is preferably amine.Yet adopt above-mentioned catalyzer to have following point: 1. palladium is expensive, thereby cost is higher; 2. palladium metal has stronger toxicity; 3. palladium is easily residual at product, thereby has influenced its application in occasions such as medicine synthesizes; 4. above-mentioned reaction has high reaction activity and high for bromo, iodo alkene and aromatic hydrocarbon usually, but for chlorinated compound, its reactive behavior is often very low; Though up to the present, the coupling product that this compound also can obtain expecting under some conditions still has many limitation; Therefore overcoming this limitation also is the technical problem of being badly in need of solution in this field.
At the problems referred to above, copper catalyst has obtained broad research.As far back as 1963, Castro etc. with the pyridine be the solvent research of carrying out the Sonogashira reaction that the copper of equivalent promotes (referring to: Synth. Commun. 1989,19,2199).1992, Okaro etc. used the cuprous iodide of 5mol% as catalyzer, with PPh
3For part, salt of wormwood are alkali, in DMF or DMSO solvent, finished under 80 ~ 120 ℃ cuprous salt catalysis truly the Sonogashira reaction (referring to: Tetrahedron Lett. 1992,33,5363).After this, people such as Venkataraman find 1, the 10-phenanthroline can be used as part be used for copper catalysis the Sonogashira reaction (referring to: Org. Lett. 2001. 3,4315; Synthesis 2005,1706).In recent years, also developed the Sonogashira reaction that a lot of other parts are used for copper catalysis, as N, the N-N-methylsarcosine (referring to: Chem. Commun. 2004,1934), triethylene diamine is (referring to J. Org. Chem. 2007,72,2053), the racemization binaphthol is (referring to J. Mol. Catal. A 2008,284,85), oxine (referring to: Eur. J. Org. Chem. 2008,4050) and 1,3-diketone (referring to Org. Lett. 2008,10,3203) etc.Yet, more than all be the catalyzed reaction of carrying out in the conventional organic solvent of nonaqueous phase, so its reaction cost is than higher, and environmental friendliness not.
About the Sonogashira of aqueous phase catalysis be reflected at professor Yang Zhen by Peking University in 2005 reported (referring to: J. Org. Chem. 2005,70,391), but its catalyzer is PdCl
2, its toxicity is big and cost is high.Reaction only has two example reports about the Sonogashira that carries out in the water of copper catalysis: an example be Zhongshan University contingency thousand associate professors report in 2007 (referring to: Synthetic Commun. 2007,37,1355).Catalyzed reaction nearly all is to carry out in microwave, and catalyst levels is big: CuI (10 mol%), PPh
3(20 mol%), alkali are salt of wormwood (200 mol%), and temperature is 120 ℃.Simultaneously, he also points out also can carry out in the water that refluxes; Halohydrocarbon is only limited to fragrant iodo thing in the substrate; Especially, to carry out in order reacting better, to have added the phase-transfer catalyst TBAB(Tetrabutyl amonium bromide of 1 equivalent in the system).Second example is that the Liu Shenghua of Wuhan University teaches in (referring to Appl. Organometal. Chem.2009,23,75) of 2009 reports, and its catalyst system is CuI (5 mol%), PPh
3(15 mol%), alkali are potassium hydroxide (200 mol%), and temperature is 140 ℃; Halohydrocarbon is only limited to fragrant iodo thing in the substrate.But its shortcoming is: catalyst levels height, temperature of reaction are too high, the substrate narrow range.
In sum, at the Sonogashira reaction that is fit to carry out in the water, or need with palladium catalyst at high price, or need under hot conditions (as 120 ~ 140 ℃), increase the difficulty of reaction and the danger of operation like this.In addition, in order to improve the yield of reaction, also need additionally to add phase-transfer catalyst, some reaction also needs to carry out in microwave reactor.In addition, present catalyst system only can satisfy the reaction of fragrant iodo thing, for low price but low slightly fragrant bromo-derivative or the chloro thing of reactive behavior is helpless.Therefore, no matter present catalyst system is from cost, or operation easier and hazard level aspect, all is to be difficult to realize large-scale application or suitability for industrialized production.
Therefore, develop the catalyst system of Yuan the coupled reaction of Yong Yu of a kind of environmental protection, no palladium, no amine, and can in water, carry out, reduce temperature of reaction, have active operation significance.
Summary of the invention
The object of the invention provides a kind of copper catalyst system of using in Yuan coupled reaction.
For achieving the above object, the technical solution used in the present invention is: the copper catalyst system of Yuan coupled reaction of a kind of Yong Yu, comprise mantoquita, phosphine part and mineral alkali, and three's mol ratio is 1:50000 ~ 200000:200000 ~ 1000000;
Described mantoquita is selected from more than one mixture of a kind of in cuprous iodide, cupric acetylacetonate, cuprous bromide, copper sulfate, the copper powder or its;
Described phosphine part is trivalent phosphine part.
Above, described trivalent phosphine part can adopt triaryl phosphine.Copper in the described copper powder is zero-valent state.
In the technique scheme, described mineral alkali is selected from a kind of in salt of wormwood, the cesium carbonate etc. or more than one mixture.
Further technical scheme, in mass, described mantoquita accounts for 1,000,000 of catalyst system/to ppm ten.The content that is mantoquita is the ppm level.
The present invention asks for protection the application that above-mentioned copper catalyst system prepares acetylene compound in a Cuiization Yuan coupled reaction simultaneously.
The present invention asks for protection above-mentioned copper catalyst system prepares acetylene compound in a Cuiization Yuan coupled reaction method simultaneously; be reactant with aryl halide, end group alkynes; catalyzer mantoquita, phosphine part, mineral alkali and reactant are dissolved in the aqueous solvent; under 60 ~ 120 ℃, react 3 ~ 48 hours preparation acetylene compounds.The mol ratio of end group alkynes and aryl halide is 1 ~ 1.5: 1, is preferably 1.2: 1.
Above, described aryl halide is iodo aromatic hydrocarbon, bromo aromatic hydrocarbon, chlorination aromatic hydrocarbon or aryl boric acid.Optimized technical scheme, when described aryl halide is bromo aromatic hydrocarbon, chlorination aromatic hydrocarbon or aryl boric acid, can add the phase-transfer catalyst of 1mol% ~ 200mol% in the above-mentioned reaction system, described phase-transfer catalyst is selected from but is not limited to: Tetrabutyl amonium bromide (TBAB), tetrabutylammonium chloride (TBAC); Be preferably TBAB.The yield that can guarantee target product like this can further improve.In addition, when described aryl halide is bromo aromatic hydrocarbon, chlorination aromatic hydrocarbon or aryl boric acid, also can add sodium iodide in the above-mentioned reaction system, the mol ratio of sodium iodide and aryl halide is 1 ~ 2: 1, can improve productive rate equally.
Further technical scheme, a Shang Shu Yuan coupled reaction is carried out in inert atmosphere.For example in atmosphere of inert gases such as argon gas or nitrogen, carry out, if reaction conditions is controlled not strict or directly carried out, be easy to generate a spot of alkynes from coupled product in air.
Because technique scheme is used, the present invention compared with prior art has following advantage:
1. the present invention has developed a kind of copper catalyst system of new Yuan coupled reaction of Yong Yu, compare with the noble metal catalyst system that contains in the past, catalyst system of the present invention has replaced precious metal with cheap mantoquita, greatly reduce cost, and mantoquita itself does not have toxicity, in addition, mantoquita is more stable in air, can not remain in the product when aftertreatment.
2. copper catalyst system of the present invention can adopt eco-friendly water as reaction solvent when advancing capable Yuan coupled reaction, and be conducive to protect environment and save cost, also be that this is reflected at the major progress in the Green Chemistry.
3. the suitable substrate a wider range of catalyst system of the present invention comprises all kinds of aryl halides and all kinds of end group alkynes, and the chemical yield of product is the highest to surpass 99%.
4. catalyst system of the present invention has very high selectivity, and no side reaction takes place, and reaction product detects through GC-MS, finds generating from coupled product of no alkynes.
5. catalyst system amount of the present invention is extremely low, and we use the catalyzer of ppm level can obtain target product efficiently, and so low consumption still belongs to the first for this reaction, have extremely important industrial application value.
6. catalyst system of the present invention can adopt triaryl phosphine cheap and easy to get as part, and temperature of reaction is lower, is easier to save cost.
Embodiment
Be further described below in conjunction with the present invention of embodiment:
Embodiment one
The CuI (0.0000005 mmol) that in a withstand voltage Schlenk test tube, packs into successively, triaryl phosphine (PPh
3) (0.02 mmol), salt of wormwood (1.0 mmol), and H
2O(3 mL); be that circulation vacuumizes and with argon replaces three times with this; under gas shield; add iodobenzene (0.5 mmol) and phenylacetylene (0.6 mmol) respectively with microsyringe; heated about 24 hours 85 ℃ oil bath this system sealing back then; add earlier the 4 mL shrends reaction of going out; use ethyl acetate extraction (4 mL * 3) then; merge organic phase and use anhydrous sodium sulfate drying; concentrate the back and can obtain coupled product 1 by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)); 2-dibenzenyl (88.5 mg), yield is 99%.Fusing point is 58 ~ 59 ℃.GC-MS show do not detect in the system of reaction back alkynes from coupled product.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.59-7.48 (m, 4H), 7.39-7.29 (m, 6H);
13C NMR (100 MHz, CDCl
3) (δ, ppm) 133.3 (CH), 130.0 (CH), 129.9 (CH), 124.9 (C), 91.0 (C); The high resolution mass spectrum data are: HRMS (ESI
+) calc for [C
14H
10]
+Requires m/z 178.0783, found 178.0791.
Embodiment two
The CuI (0.0000005 mmol) that in a withstand voltage Schlenk test tube, packs into successively, PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and H
2O(3 mL), be that circulation vacuumizes and with argon replaces three times, under gas shield, adds respectively chloroiodobenzone (0.5 mmol) and phenylacetylene (0.6 mmol) with microsyringe with this.Heated about 24 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 4-chlorobenzene acetylenylbenzene (105.2 mg) by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), yield is 98%.Fusing point is 83 ~ 84 ℃.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.53 (t, J=7.6 Hz, 2H), 7.46 (d, J=8.4 Hz, 2H), 7.36-7.34 (m, 4H), 7.32 (s, 1H);
13C NMR (CDCl
3, 100 MHz) and (δ, ppm) 135.9 (C), 134.5 (CH), 133.3 (CH), 130.3 (CH), 130.1 (CH), 130.0 (CH), 124.6 (C), 123.4 (C), 91.9 (C), 89.9 (C); The high resolution mass spectrum data are: HRMS (ESI
+) calc for [C
14H
10]
+Requires m/z 212.0393, found 212.0396.
Embodiment three
The CuI (0.0000005 mmol) that in a withstand voltage Schlenk test tube, packs into successively, PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and H
2O(3 mL), be that circulation vacuumizes and with argon replaces three times, under gas shield, adds respectively methoxyl group iodobenzene (0.5 mmol) and 4-fluorobenzene acetylene (0.6 mmol) with microsyringe with this.Heated about 24 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain cross-coupling product 1 fluoro-4-(2-(4-anisole) ethynyl) benzene (113.1 mg) by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), yield is 99%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 3.84 (s, OCH
3), 6.89 (d, J=8.8 Hz, 2H, ArH), 7.02-7.06 (m, 2H, ArH), 7.46-7.51 (m, 4H, ArH);
13C NMR (CDCl
3, 75 MHz) and (δ, ppm) 164.2 (d, J=247.5 Hz, C), 159.9 (CH), 133.5 (d, J=7.5 Hz, CH), 133.2 (CH), 119.9 (C), 115.9 (d, J=22.5 Hz, CH), 115.4 (C), 114.2 (C), 89.2 (C), 87.2 (C), 55.5 (OCH
3); The high resolution mass spectrum data are: HRMS (ESI
+) calc for [C
15H
11FO]
+Requires m/z 226.0794, found 220.0704.
Embodiment four
The CuI (0.0000005 mmol) that in a withstand voltage Schlenk test tube, packs into successively, PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and H
2O(3 mL), be that circulation vacuumizes and with argon replaces three times, under gas shield, adds iodobenzene (0.5 mmol) and 4-fluorobenzene acetylene (0.6 mmol) respectively with microsyringe with this.Heated about 24 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 4-fluorobenzene acetylenylbenzene (96.1 mg) by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), yield is 98%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.53-7.50 (m, 4H, ArH), 7.36-7.34 (m, 3H, ArH), 7.05 (t, J=8.6 Hz, 2H, ArH);
13C NMR (CDCl
3, 100 MHz) and (δ, ppm) 165.4 (d, J=249.5 Hz, C), 135.2 (d, J=8.3 Hz, CH), 133.2 (CH), 130.0 (d, J=3.7 Hz, CH), 124.7 (C), 121.0 (d, J=3.4 Hz, CH), 117.4 (C), 117.2 (C), 90.7 (C), 89.2 (C); The high resolution mass spectrum data are: HRMS (ESI
+) calc for [C
14H
9F]
+Requires m/z 196.0688, found 196.0690.
Embodiment five
The CuI (0.0000005 mmol) that in a withstand voltage Schlenk test tube, packs into successively, PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and H
2O(3 mL), be that circulation vacuumizes and with argon replaces three times, under gas shield, adds respectively chloroiodobenzone (0.5 mmol) and 4-fluorobenzene acetylene (0.6 mmol) with microsyringe with this.Heated about 48 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 1-chloro-4-(2-(4-fluorobenzene) ethynyl) benzene (111.9 mg) by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), yield is 97%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.06 (t, J=8.8 Hz, 2H, ArH), 7.33 (d, J=8.4 Hz, 2H, ArH), 7.45 (d, J=8.4 Hz, 2H, ArH), 7.49-7.53 (m, 2H, ArH);
13C NMR (CDCl
3, 100 MHz) and (δ, ppm) 165.5 (d, J=249.9 Hz, C), 136.0 (C), 135.2 (J=8.3 Hz, CH), 134.4 (CH), 130.4 (CH), 123.2 (C), 120.6 (d, J=3.5 Hz, CH), 117.5 (d, J=21.1 Hz, C), 90.9 (C), 89.5 (C); The high resolution mass spectrum data are: HRMS (ESI
+) calc for [C
14H
8FCl]
+Requires m/z 230.0299, found 230.0300.
Embodiment six
With above CuI/ PPh
3/ salt of wormwood/H
2The O catalyst system is used for the linked reaction to methoxyl group iodobenzene (0.5 mmol) and 4-methylbenzene acetylene (0.6 mmol), stirs at 85 ℃ and obtains coupled product 1-methoxyl group-4-(2-p-phenylacetylene base) benzene (107.8 mg) in 24 hours, and yield is 97%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.47 – 7.39 (m, 4H, ArH), 7.14 (d, J=8.0 Hz, 2H, ArH), 6.87 (d, J=8.4 Hz, 2H, ArH), 3.83 (s, 3H, OCH
3), 2.36 (s, 3H, CH
3);
13C NMR (CDCl
3, 75 MHz) and (δ, ppm) 159.7 (C), 138.2 (C), 133.2 (CH), 131.2 (CH), 129.5 (CH), 120.7 (CH), 115.8 (C), 114.2 (C), 88.9 (C), 88.4 (C), 55.5 (OCH
3), 21.7 (CH
3); The high resolution mass spectrum data are: HRMS (ESI
+) calc for [C
16H
14O]
+Requires m/z 222.1045, found 222.1042.
Embodiment seven
With above CuI/ PPh
3/ salt of wormwood/H
2The O catalyst system is used for the linked reaction to methyl iodobenzene (0.5 mmol) and 4-benzene butine (0.6 mmol), stirs at 85 ℃ and obtains coupled product 1-methoxyl group-4-(4-benzene butyl-1-alkynes) benzene (92.2 mg) in 12 hours, and yield is 95%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.32 – 7.25 (m, 7H, ArH), 6.81 (d, J=8.4 Hz, 2H, ArH), 3.79 (s, 3H, OCH
3), 2.92 (t, J=7.6 Hz, 2H, ArCH
2), 2.67 (t, J=7.6 Hz, 2H, CH
2).
Embodiment eight
With above CuI/ PPh
3/ salt of wormwood/H
2The O catalyst system is used for the linked reaction to methyl iodobenzene (0.5 mmol) and 1-octyne (0.6 mmol), stirs at 85 ℃ and obtains coupled product 1-(certain herbaceous plants with big flowers alkane-1-alkynes) benzene (83.3 mg) in 12 hours, and yield is 97%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm): 7.35 (d, J=8.8 Hz, 1H), 6.95 (d, J=8.8 Hz, 1H), 6.87 – 6.81 (m, 2H), 3.80 (s, 3H), 2.38 (t, J=7.2 Hz, 2H), 1.63 (t, J=7.2 Hz, 2H), 1.58 (d, J=7.2 Hz, 2H), 1.48 (d, J=7.2 Hz, 2H), 1.44 – 1.40 (m, 2H), 0.94 – 0.90 (m, 3H);
13C NMR (100 MHz, CDCl
3) δ: 134.5 (CH), 121.1 (CH), 116.4 (CH), 115.4 (CH), 90.4 (C), 88.4 (C), 56.8 (CH
3), 33.0 (CH
2), 30.5 (CH
2), 30.3 (CH
2), 24.2 (CH
2), 21.0 (CH
2), 15.7 (CH
3).
Embodiment nine
The CuI (0.0000005 mmol) that in a Schlenk test tube, packs into successively, PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), sodium iodide (1.0 mmol) and H
2O(3 mL), be that circulation vacuumizes and with argon replaces three times, under gas shield, adds respectively methoxyl group bromobenzene (0.5 mmol) and phenylacetylene (0.6 mmol) with microsyringe with this.Heated about 24 hours 120 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 4-anisole acetylenylbenzene (75.1mg) by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), yield is 72%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.52 – 7.50 (m, 2 H, ArH), 7.47 (d, J=8.8 Hz, 2 H, ArH), 7.36 – 7.32 (m, 3 H, ArH), 6.88 (d, J=8.8 Hz, 2 H, ArH), 3.83 (s, 3 H, CH
3);
13C NMR (CDCl
3, 100 MHz) and (δ, ppm) 161.2 (C), 134.7 (CH), 133.1 (CH), 130.0 (CH), 129.6 (C), 125.2 (CH), 117.0 (C), 115.6 (CH), 91.0 (C), 89.7 (C), 56.9 (CH); The high resolution mass spectrum data are: HRMS (ESI
+) calc for [C
15H
12O]
+Requires m/z 208.0888, found 208.0896.
Embodiment ten
The CuI (0.0000005 mmol) that in a Schlenk test tube, packs into successively, PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and H
2O(3 mL), be that circulation vacuumizes and with argon replaces three times, under gas shield, adds a diiodo-benzene (0.5 mmol) and phenylacetylene (2.5 mmol) respectively with microsyringe with this.Heated about 24 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 1 by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), 3-tolane base benzene (135.0 mg), yield is 97%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.39-7.32 (m, 7H, ArH), 7.49 (d, J=7.6 Hz, 2H, ArH), 7.54 (t, J=3.6 Hz, 4H, ArH), 7.72 (s, 1H, ArH);
13C NMR (CDCl
3, 100 MHz) and (δ, ppm) 136.2 (CH), 133.3 (CH), 132.9 (CH), 130.1 (CH), 130.1 (CH), 130.1 (CH), 125.2 (C), 124.6 (C), 91.6 (C), 90.2 (C); The high resolution mass spectrum data are: HRMS (ESI
+) calc for [C
22H
14]
+Requires m/z 278.1096, found 278.1096.
Embodiment 11
CuI (0.00005 mmol) successively packs in a Schlenk test tube; three (1-naphthyl) phosphine (0.02 mmol); salt of wormwood (1.0 mmol); and water (3 mL); be that circulation vacuumizes and with argon replaces three times with this; under gas shield, add iodobenzene (0.5 mmol) and phenylacetylene (0.6 mmol) respectively with microsyringe.Heated about 12 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 1 by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), 2-dibenzenyl (78.5 mg), yield is 99%.Fusing point is 58-59 ℃.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.59-7.48 (m, 4H), 7.39-7.29 (m, 6H);
13C NMR (100 MHz, CDCl
3) (δ, ppm) 133.3 (CH), 130.0 (CH), 129.9 (CH), 124.9 (C), 91.0 (C); The high resolution mass spectrum data are: HRMS (ESI
+) calc for [C
14H
10]
+Requires m/z 178.0783, found 178.0791.
Embodiment 12
Cu (OTf) successively packs in a Schlenk test tube
2(0.0000005 mmol), PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and water (3 mL) are that circulation vacuumizes and with argon replaces three times, under gas shield, adds iodobenzene (0.5 mmol) and phenylacetylene (0.6 mmol) respectively with microsyringe with this.Heated about 12 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 1 by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), 2-dibenzenyl (64.2 mg), yield is 91%.Fusing point is 58-59 ℃.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.59-7.48 (m, 4H), 7.39-7.29 (m, 6H);
13C NMR (100 MHz, CDCl
3) (δ, ppm) 133.3 (CH), 130.0 (CH), 129.9 (CH), 124.9 (C), 91.0 (C); The high resolution mass spectrum data are: HRMS (ESI
+) calc for [C
14H
10]
+Requires m/z 178.0783, found 178.0791.
Embodiment 13:
CuSO successively packs in a Schlenk test tube
45H
2O (0.0000005 mmol), PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and water (3 mL) are that circulation vacuumizes and with argon replaces three times, under gas shield, adds iodobenzene (0.5 mmol) and phenylacetylene (0.6 mmol) respectively with microsyringe with this.Heated about 12 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 1 by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), 2-dibenzenyl (58.9 mg), yield is 66%.Fusing point is 58-59 ℃.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.59-7.48 (m, 4H), 7.39-7.29 (m, 6H);
13C NMR (100 MHz, CDCl
3) (δ, ppm) 133.3 (CH), 130.0 (CH), 129.9 (CH), 124.9 (C), 91.0 (C); The high resolution mass spectrum data are: HRMS (ESI
+) calc for [C
14H
10]
+Requires m/z 178.0783, found 178.0791.
Embodiment 14
The CuI (0.0000005 mmol) that in a Schlenk test tube, packs into successively, PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and water (3 mL) are that circulation vacuumizes and with argon replaces three times, under gas shield, adds 1-iodine naphthalene (0.5 mmol) and phenylacetylene (0.6 mmol) respectively with microsyringe with this.Heated about 24 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 1-(2-phenylacetylene base) naphthalene (113.0 mg) by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), yield is 99%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, and ppm) 8.45 (d, J=8.0 Hz, 1H, ArH), 7.88 – 7.76 (m, 3H, ArH), 7.67 – 7.59 (m, 3H, ArH), 7.56 – 7.54 (m, 2H, ArH), 7.48 – 7.39 (m, 3H, ArH);
13C NMR (100 MHz, CDCl
3) (δ, ppm) 134.9 (C), 134.8 (C), 133.3 (C), 132.0 (CH), 130.4 (CH), 130.1 (CH), 130.1 (CH), 130.0 (CH), 128.5 (CH), 128.1 (CH), 127.9 (CH), 127.0 (CH), 125.0 (CH), 122.5 (C), 95.9 (C), 89.2 (C); The high resolution mass spectrum data are: HRMS (ESI
+) calc for [C
18H
12]
+Requires m/z 228.0939, found 228.0938.
Embodiment 15 1-(trifluoromethyl)-3-(2-phenylethynyl) benzene
With CuI/ PPh
3/ salt of wormwood/TBAB (1.0 mmol)/H
2The O catalyst system is used for the linked reaction of 3-methyl bromobenzene trifluoride (0.5 mmol) and phenylacetylene (0.6 mmol), stirs at 120 ℃ and obtains coupled product 1-(trifluoromethyl)-3-(2-phenylacetylene base) benzene (115.7 mg) in 48 hours, and yield is 94%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, and ppm) 7.80 (s, 1H, ArH), 7.70 (d, J=7.6Hz, 2H, ArH), 7.59-7.54 (m, 3H, ArH), 7.48 (t, J=8.0 Hz, 1H, ArH), 7.37 (t, J=3.2 Hz, 3H, ArH);
13C NMR (100 MHz, CDCl
3) (δ, ppm) 136.2 (C), 134.1 (CH), 133.3 (CH), 130.4 (q, J=186 Hz), 130.1 (C), 130.0 (C), 129.9 (CH), 126.7 (CH), 126.4 (q, J=44 Hz), 125.9 (CH), 124.2 (CH), 92.5 (C), 89.4 (C); The high resolution mass spectrum data are: HRMS (ESI
+) calc for [C
15H
9F]
+Requires m/z 246.0656, found 246.0653.
Embodiment 16
The CuI (0.0000005 mmol) that in a Schlenk test tube, packs into successively, PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and water (3 mL) are that circulation vacuumizes and with argon replaces three times, under gas shield, adds 3-methoxyl group iodobenzene (0.5 mmol) and phenylacetylene (0.6 mmol) respectively with microsyringe with this.Heated about 24 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 3-anisole acetylenylbenzene (102.0 mg) by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), yield is 99%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.55 – 7.52 (m, 2H, ArH), and 7.37 – 7.34 (m, 3H, ArH), 7.27 – 7.23 (m, 1H, ArH), 7.13 (d, J=7.6 Hz, 2H, ArH), 7.06 (s, 1H, ArH), 6.91 – 9.88 (m, 1H, ArH), 2.82 (s, 3H, OCH3);
13C NMR (100 MHz, CDCl
3) (δ, ppm) 161.0 (C), 133.3 (CH), 131.1 (CH), 130.0 (CH), 130.0 (CH), 125.9 (CH), 125.8 (C), 124.8 (CH), 117.9 (C), 116.6 (CH), 90.9 (C), 90.8 (C), 56.9 (CH); The high resolution mass spectrum data are: HRMS (ESI
+): calcd. for [C
15H
12O]
+Requires m/z 208.0888, found 208.0884.
Embodiment 17
The CuI (0.0000005 mmol) that in a Schlenk test tube, packs into successively, PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and water (3 mL) are that circulation vacuumizes and with argon replaces three times, under gas shield, adds 2-methoxyl group iodobenzene (0.5 mmol) and phenylacetylene (0.6 mmol) respectively with microsyringe with this.Heated about 24 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 2-anisole acetylenylbenzene (102.0 mg) by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), yield is 99%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.67 – 7.64 (m, 2H, ArH), 7.58 (d, J=7.6 Hz, 1H, ArH), 7.42 – 7.39 (m, 4H, ArH), 7.04 – 6.97 (m, 2H, ArH), 3.99 (s, 3H, OCH3);
13C NMR (100 MHz, CDCl
3) (δ, ppm) 161.5 (C), 135.2 (CH), 133.3 (CH), 131.4 (CH), 129.9 (CH), 129.8 (CH), 125.2 (CH), 122.1 (C), 114.0 (C), 112.3 (CH), 95.1 (C), 87.4 (C), 57.5 (CH); The high resolution mass spectrum data are: HRMS (ESI
+): calcd. for [C
15H
12O]
+Requires m/z 208.0888, found 208.1000.
Embodiment 18
The CuI (0.0000005 mmol) that in a Schlenk test tube, packs into successively, PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and water (3 mL) are that circulation vacuumizes and with argon replaces three times, under gas shield, adds 4-nitro iodobenzene (0.5 mmol) and phenylacetylene (0.6 mmol) respectively with microsyringe with this.Heated about 24 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 4-nitrobenzene acetylene base benzene (100.0 mg) by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), yield is 91%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 8.24 (d, J=8.4 Hz, 2H), 7.69 (d, J=8.4 Hz, 2H), 7.57 – 7.60 (m, 2H), 7.41 – 7.42 (m, 3H);
13C NMR (100 MHz, CDCl
3) (δ, ppm) 148.6 (C), 133.9 (CH), 133.5 (CH), 131.9 (CH), 130.9 (CH), 130.2 (CH), 125.3 (C), 123.7 (C), 96.3 (C), 89.2 (C); The high resolution mass spectrum data are: HRMS (ESI
+): calcd. for [C
14H
9NO
2]
+Requires m/z 223.0633, found 223.0635.
Embodiment 19
The CuI (0.0000005 mmol) that in a Schlenk test tube, packs into successively, PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and water (3 mL) are that circulation vacuumizes and with argon replaces three times, under gas shield, adds 4-amino iodobenzene (0.5 mmol) and phenylacetylene (0.6 mmol) respectively with microsyringe with this.Heated about 24 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 4-amino-benzene acetylenylbenzene (93.0 mg) by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), yield is 96%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.54 (d, J=6.4 Hz, 2H, ArH), 7.38 – 7.32 (m, 5H, ArH), 7.64 (d, J=6.4 Hz, 2H, ArH), 3.77 (s, 2H, NH
2);
13C NMR (100 MHz, CDCl
3) (δ, ppm) 139.5 (C), 134.6 (CH), 133.0 (CH), 130.0 (CH), 129.4 (CH), 119.0 (CH), 116.4 (C), 114.1 (C), 91.9 (C), 89.0 (C); The high resolution mass spectrum data are: HRMS (ESI
+): calcd. for [C
14H
11N]
+Requires m/z 193.0891, found 193.0892.
Embodiment 20
The CuI (0.0000005 mmol) that in a Schlenk test tube, packs into successively, PPh
3(0.02 mmol); salt of wormwood (1.0 mmol), and water (3 mL) are that circulation vacuumizes and with argon replaces three times with this; under gas shield, add 4-methyl-formiate base iodobenzene (0.5 mmol) and phenylacetylene (0.6 mmol) respectively with microsyringe.Heated about 24 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 4-methyl-formiate base phenylacetylene base benzene (93.0 mg) by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), yield is 79%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 8.03 (d, J=8.0 Hz, 2H, ArH), 7.59 (d, J=8.0 Hz, 2H, ArH), 7.57 – 7.54 (m, 2H, ArH), 7.38 – 7.36 (m, 3H, ArH), 3.92 (s, 3H, CH
3);
13C NMR (100 MHz, CDCl
3) (δ, ppm) 168.2 (C), 133.4 (CH), 133.1 (CH), 131.1 (CH), 130.4 (CH), 130.1 (CH), 129.9 (CH), 129.6 (C), 124.3 (C), 94.0 (C), 90.3 (C), 53.9 (CH
3); The high resolution mass spectrum data are: HRMS (ESI
+): calcd. for [C
16H
12O
2]
+Requires m/z 236.0837, found 236.0837.
Embodiment 21
The CuI (0.0000005 mmol) that in a Schlenk test tube, packs into successively, PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and water (3 mL) are that circulation vacuumizes and with argon replaces three times, under gas shield, adds 4-ethanoyl iodobenzene (0.5 mmol) and phenylacetylene (0.6 mmol) respectively with microsyringe with this.Heated about 24 hours 85 ℃ oil bath this system sealing back then; add earlier the 4 mL shrends reaction of going out; use ethyl acetate extraction (4 mL * 3) then; merge organic phase and use anhydrous sodium sulfate drying; concentrate the back and can obtain coupled product 4-acetylbenzene acetylenylbenzene (105.0 mg) by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), yield is 98%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.95 (d, J=8.0 Hz, 2H, ArH), 7.62 (d, J=8.0 Hz 2H, ArH), 7.57 – 7.56 (m, 2H, ArH), 7.38 (s, 3H, ArH), 2.62 (s, 3H, CH3);
13C NMR (100 MHz, CDCl
3) (δ, ppm) 199.0 (C), 137.7 (C), 133.4 (CH), 133.3 (CH), 130.5 (CH), 130.1 (CH), 129.9 (CH), 129.8 (C), 124.2 (C), 94.3 (C), 90.2 (C), 28.3 (CH
3) the high resolution mass spectrum data are: HRMS (ESI
+): calcd. for [C
16H
12O]
+Requires m/z 220.0888, found 220.0887.
Embodiment 22
The CuI (0.0000005 mmol) that in a Schlenk test tube, packs into successively, PPh
3(0.02 mmol), salt of wormwood (1.0 mmol), and water (3 mL) are that circulation vacuumizes and with argon replaces three times, under gas shield, adds 1-bromstyrol (0.5 mmol) and phenylacetylene (0.6 mmol) respectively with microsyringe with this.Heated about 24 hours 85 ℃ oil bath this system sealing back then, add earlier the 4 mL shrends reaction of going out, use ethyl acetate extraction (4 mL * 3) then, merge organic phase and use anhydrous sodium sulfate drying, concentrate the back and can obtain coupled product 1-styryl-2-phenylacetylene (96.0 mg) by simple column chromatography (eluent uses sherwood oil (60 ~ 90 ℃)), yield is 94%.Its nuclear magnetic data is:
1H NMR (CDCl
3, 400MHz) (δ, ppm) 7.47 (m, 2H, ArH), 7.42 (d, J=7.2 Hz, 2H), 7.36-7.29 (m, 6H, ArH); The high resolution mass spectrum data are: HRMS (ESI
+): calcd. for [C
16H
12]
+Requires m/z 204.0939, found 204.0939.
Claims (5)
1. one kind with in the copper catalyst system of Yuan coupled reaction, and it is characterized in that: be made up of mantoquita, phosphine part and mineral alkali, three's mol ratio is 1:50000 ~ 200000:200000 ~ 1000000;
Described mantoquita is selected from more than one mixture of a kind of in cuprous iodide, cupric acetylacetonate, cuprous bromide, the copper sulfate or its;
Described phosphine part is triaryl phosphine.
2. the copper catalyst system of Yuan coupled reaction of Yong Yu according to claim 1 is characterized in that: described mineral alkali is selected from a kind of in salt of wormwood, the cesium carbonate or more than one mixture.
3. the described copper catalyst system of claim 1 prepares application in the acetylene compound in a Cuiization Yuan coupled reaction.
4. application rights requires 1 described copper catalyst system to prepare the method for acetylene compound in a Cuiization Yuan coupled reaction, it is characterized in that: be reactant with aryl halide, end group alkynes, catalyzer mantoquita, phosphine part, mineral alkali and reactant are dissolved in the aqueous solvent, under 60 ~ 120 ℃, react 3 ~ 48 hours preparation acetylene compounds.
5. method according to claim 4 is characterized in that a: Yuan coupled reaction carries out in inert atmosphere.
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| 《COPPER-CATALYZED COUPLING REACTION OF ARYL AND VINYL HALIDES WITH TERMINAL ALKYNES》;Kazumi Okuro,et al.;《Tetrahedron Letters》;19920908;第33卷(第37期);5363-5364 * |
| Kazumi Okuro,et al..《COPPER-CATALYZED COUPLING REACTION OF ARYL AND VINYL HALIDES WITH TERMINAL ALKYNES》.《Tetrahedron Letters》.1992,第33卷(第37期),5363-5364. |
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