CN102936266A - Synthesis of pH-responding palladium N-heterocyclic carbene chelate and catalytic application thereof - Google Patents
Synthesis of pH-responding palladium N-heterocyclic carbene chelate and catalytic application thereof Download PDFInfo
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Abstract
The invention provides synthesis of a pH-responding palladium N-heterocyclic carbene chelate and catalytic application thereof. The synthesis process consists of: taking dimethyl sulfoxide as a solvent, adding palladium acetate and a benzoate-containing dibromodiimidazole ionic salt, leaving them to react for 12h at 60DEG C, then raising the temperature to 130DEG C to make them further react for 2h, conducting concentration, carrying out washing with tetrahydrofuran, and performing vacuum drying to obtain a water insoluble N-heterocyclic carbene chelate of palladium; and hydrolyzing the ester group in the chelate by lithium hydroxide, then conducting acidification with hydrochloric acid or hydrobromic acid, thus obtaining the pH-responding palladium N-heterocyclic carbene chelate. The palladium N-heterocyclic carbene chelate synthesized in the invention contains a carboxyl group and has a pH-responding function. The palladium N-heterocyclic carbene chelate has high catalytic activity to the coupling reaction of aryl halides in water, and a catalyst can be separated by adjusting the pH of the reaction system and can be recycled repeatedly. The catalytic system is environment-friendly, thus providing a new path for development of organometallic chemistry and application of N-heterocyclic carbine compounds.
Description
Technical field
The present invention relates to the synthetic and catalytic applications of the palladium N-heterocycle carbine inner complex of pH response.
Background technology
Transition metal-catalyzed aryl halide and the cross-coupling reaction of organometallic reagent are a kind of effective means that realizes C-C, carbon-nitrogen bond coupling, playing the part of extremely important role in producing in that the industry of dyestuff, medicine, agricultural chemicals, daily chemicals and superpolymer is synthetic, be widely used in natural product, pharmaceutical intermediate and functional materials synthetic.The focus of research concentrates in non-phosphine part and the eco-friendly reaction medium at present, particularly score linked reaction in the water.Inexpensive, nontoxic, not flammable, easy recovery that glassware for drinking water has, unique advantage such as free from environmental pollution.Water also for linked reaction provides new reaction environment, improves selectivity, the transformation efficiency of reaction and improves except can replacing organic solvent, reduce polluting, and also makes the operating process such as separating-purifying simple and easy to do.Because most of organic compound solubleness in water is very low, some compound or title complex be very easily hydrolysis or decomposition in water, and this has hindered popularization and the development of water organic reaction.Therefore, design efficient water soluble catalyzer is the key that realizes that the water medium linked reaction is carried out.Various nitrogenous water soluble ligands are designed synthetic and are applied to cross-coupling reaction in the water medium.Although the N-heterocyclic carbine compound of palladium has fabulous water and air stability, the linked reaction of catalysis is studied widely in organic solvent, and it is less that the catalystic converter system research in water medium is in the news.
Summary of the invention
The object of the invention is to overcome the prior art deficiency, a kind of synthetic and catalytic applications of palladium N-heterocycle carbine inner complex of aqueous phase pH response is provided.
The present invention adopts following technical scheme:
The palladium N-heterocycle carbine inner complex of pH response be two N-heterocycle carbine compounds take the acid functionalization of 4-substituted benzoyl as part, two halogen atoms of connection or Pyridine Molecules on the palladium atom, its molecular formula is:
Its R is chlorine atom, bromine atoms or Pyridine Molecules.
The preparation method of the N-heterocycle carbine inner complex of the palladium of pH response: take methyl-sulphoxide as solvent, the acid chloride and the two imidazol ion salt part that add mol ratio 1:1,60 degrees centigrade of stirrings are warming up to 130 degrees centigrade and continue reaction 2 hours after 12 hours, concentrated, with tetrahydrofuran (THF) washing 3 times, vacuum-drying obtains non-water-soluble palladium N-heterocycle carbine inner complex; In the solvent of first alcohol and water, after the hydrolysis of adding lithium hydroxide, add hydrochloric acid or Hydrogen bromide acidifying, wash solid with water the final vacuum drying, get the palladium N-heterocycle carbine inner complex of pH response.
The present invention can be used for the cross-coupling reaction of aryl halide and aryl boric acid in the water medium, has formed undersized Pd nano particle in the reaction process, and can reclaim catalyzer by the pH of conditioned reaction system, and can recycle.For the development of Organometallic Chemistry and N-heterocyclic carbine compound provides a new route.
Description of drawings
The transmission electron microscope picture of the palladium nanoparticle that Fig. 1 embodiment of the invention 12 makes.
The catalytic cycle response diagram of Fig. 2 embodiment of the invention 13 and embodiment 14.
Fig. 3 pH response of the present invention picture.
Fig. 4 the present invention is based on the pH response picture of embodiment 7.
Embodiment
To help to understand the present invention by following examples of implementation, but not limit content of the present invention.
Embodiment 1,
Under the room temperature, under nitrogen protection, with part
L1(0.3g, 0.5mmol) and acid chloride (0.1g, 0.5 mmol) join in the 5.0mL methyl-sulphoxide.Stir, be heated to 60 degrees centigrade of reactions and be warming up to 130 degrees centigrade of continuation reactions 2 hours after 12 hours.After the cooling, to doing, obtain the N-heterocycle carbine inner complex of palladium, productive rate 86 %s with 3 final vacuum dryings of tetrahydrofuran (THF) washing at 90 degrees centigrade of vacuum concentration.
?1H?NMR(400?MHz,
d6-DMSO):?δ?8.3-7.8?(m,?12H),?6.7-6.5?(m,?2H),?4.39?(q,?
J?=?6.8?Hz,4H),?1.39?(t,?
J?=?7.2?Hz,?4H);
13C?NMR(100?MHz,
d6-DMSO):?δ?165.8,?159.9,?143.4,?130.5,?129.8,?125.9,?123.2,?61.5,?14.7.
Embodiment 2,
Under the room temperature, will
1(0.3g, 0.4mmol) and lithium hydroxide (0.05g, 1.3 mmol) join in the mixed solvent of 3 mL methyl alcohol and 3 mL water, behind the stirring reaction 2 hours, concentrate and remove methyl alcohol, in the ice-water bath, be acidified to pH value to 4 with dilute hydrobromic acid, the adularescent solid is separated out, and white solid is washed respectively twice with 5mL water and 5mL tetrahydrofuran (THF) successively, and vacuum-drying gets the palladium N-heterocycle carbine inner complex of white pH response
2, productive rate 80 %;
1H NMR (400 MHz,
d6-DMSO): δ 8.30-8.15 (m, 4H), 8.00-7.80 (m, 8H), 6.60-6.45 (m, 2H);
13C NMR (100 MHz,
d6-DMSO): δ 167.3,159.9,143.1,130.9,130.6,125.7,123.1. ultimate analysis theoretical value: C
21H
16Br
2N
4O
4PdH
2O (672.6): C 37.50, and H 2.70, and N 8.33, ultimate analysis observed value: C 37.48, and H 2.89, N 8.21 %.
Embodiment 3,
Under the room temperature, will
1(0.3g, 0.4mmol) and lithium hydroxide (0.05g, 1.3 mmol) join in the mixed solvent of 3 mL methyl alcohol and 3 mL water, behind the stirring reaction 2 hours, concentrate and remove methyl alcohol, in the ice-water bath, be acidified to pH value to 4 with dilute hydrochloric acid, the adularescent solid is separated out, and white solid is washed respectively twice with 5mL water and 5mL tetrahydrofuran (THF) successively, and vacuum-drying gets the palladium N-heterocycle carbine inner complex of white pH response
3, productive rate 73 %;
1H NMR (400 MHz,
d6-DMSO): δ 8.30-8.15 (m, 4H), 8.10-7.80 (m, 8H), 6.60-6.45 (m, 2H);
13C NMR (100 MHz,
d6-DMSO): δ 167.3,158.6,143.0,130.8,130.6,125.5,125.5,123.2,123.0. ultimate analysis theoretical value: C
21H
16BrClN
4O
4Pd0.5H
2O (619.2): C 40.74, and H 2.77, and N 9.05, ultimate analysis observed value: C 40.76, and H 2.97, N 8.95 %.
Embodiment 4,
With title complex
3(0.1g, 0.2 mmol) be dissolved in the 20mL methyl alcohol of the pyridine that contains 2mL, reflux obtained settled solution after 2 hours, room temperature was placed after 48 hours, add the 50mL ether, separate out white solid, white solid is used respectively 5mL ether and 5mL water washing, then vacuum-drying gets the palladium N-heterocycle carbine inner complex of white pH response
4, productive rate 91 %;
1H NMR (400 MHz,
d6-DMSO): δ 8.57 (s, 1H), 8.30-8.15 (m, 6H), 8.10-7.90 (m, 9H), 7.85-7.75 (m, 2H), 7.73-7.67 (t,
J=7.6Hz, 1H), 7.60-7.55 (m, 1H), 7.41-7.36 (m, 1H), 7.12 (t,
J=6.8Hz, 1H), 6.80 (q,
J=12.8Hz, 2H);
13C NMR (100 MHz,
d6-DMSO): δ 167.0,167.0, and 166.5,157.7,155.1,151.5,149.7,142.3,140.8,138.6,136.3,131.8,131.2,130.5,130.2,125.5,125.1,124.8,1241,123.4,123.0,122.9,65. ultimate analysis theoretical value: C
21H
14N
4O
4Pd3.5H
2O (555.8): C 45.38, and H 3.81, and N 10.08, ultimate analysis observed value: C 45.39, and H 3.73, N 10.18 %.
Embodiment 5,
Under the room temperature, will
4(0.1g, 0.2mmol) is dissolved in the methyl-sulphoxide, adds dilute hydrochloric acid and is acidified to pH to 4, separates out white solid, and respectively with 5mL water and the washing of 5mL tetrahydrofuran (THF), vacuum-drying gets the palladium N-heterocycle carbine inner complex of white pH response with white solid
5, productive rate 80 %.TD:355
oC;
1H NMR (400 MHz,
d6-DMSO): 8.18 (d,
J=8.4 Hz, 4H), 7.95 (d,
J=8.4 Hz, 4H), 7.88 (d,
J=2 Hz, 2H), 7.82 (d,
J=2 Hz, 2H), 6.53 (q,
J=15.2 Hz, 2H);
13C NMR (400 MHz,
d6-DMSO): δ 167.3,158.6,143.0,130.8,130.6,125.5,123.2,123.0. ultimate analysis theoretical value: C
21H
16C
L2N
4O
4Pd3.5H
2O (628.8): C 40.11, and H 3.69, and N 8.91, ultimate analysis observed value: C 40.21, and H 3.56, N 8.88 %.
Embodiment 6,
Under the room temperature, in a sealed tube, with 4-imidazoles phenylformic acid (2.0g, 9.0mmol) and methylene bromide (0.8g, 4.3mmol) join in the 10mL tetrahydrofuran (THF), with reaction in 130 degrees centigrade the oil bath 24 hours, a large amount of white solids were separated out in cooling, white solid is washed with the cold tetrahydrofuran (THF) of 5mL, and vacuum-drying gets part
L1, productive rate 78 %.
1H?NMR?(400?MHz,?
d6-DMSO):?δ?10.49?(s,?2?H),?8.56?(s,?2?H),?8.50?(s,?2H),?8.25?(d,?
J?=?8.8?Hz,?4H),?8.02?(d,?
J?=?8.8?Hz,?4H),?6.97?(s,?2H),?4.37?(q,?
J?=?7.2?Hz,?4H),?1.36?(t,?
J?=?7.2?Hz,?6?H);
13C?NMR(100?MHz,?
d6-DMSO):?δ?165.0,?138.4,?138.2,?131,7,?131,6,?123,7,?122.7,?121.9,?61.9,?59.1,?14.6.
Embodiment 7-11
In the pure water, with the palladium N-heterocycle carbine inner complex of pH response
4As the catalytic applications of catalyzer to the cross-coupling of aryl halide and aryl boric acid.
Embodiment 7
The preparation of 4-biphenyl ethyl ketone
Under the air conditions, in a reaction tubes, add successively 4-bromoacetophenone (199.0 mg, 1.0 mmol), phenylo boric acid (183.0 mg, 1.5 mmol), salt of wormwood (276.0 mg, 2.0 mmol), Tetrabutyl amonium bromide (322.0 mg, 1.0 mmol), catalyzer
4(0.7 mg, 0.1 mol%), water (2.0 mL) is as reaction solvent, in 100
oReaction is 2 hours in the C oil bath, and 3 mL ethyl acetate extractions are used in cooling at every turn, triplicate with behind the anhydrous sodium sulfate drying, concentrates to get crude product after organic phase merges, silicagel column separates (leacheate is sherwood oil), gets 196mg product 4-biphenyl ethyl ketone, productive rate 100%.
1H?NMR(CDCl
3,?400?MHz):?δ?8.06?(d,?
J?=8.4?Hz,?2H),?7.71?(d,?
J?=?8.4Hz,?2H),?7.65?(d,?
J?=?7.2?Hz,?2H),?7.50?(t,?
J?=?7.2?Hz,?2H),?7.43?(t,?
J?=?7.2?Hz,?1H),?2.67?(s,?3H);?
13C?NMR(CDCl
3,?100?MHz):?δ?197.8,?145.8,?139.9,?135.9,?129.0,?128.9,?128.3,?127.3,?127.2,?26.7.
Embodiment 8,
The preparation of 4-fluorine biphenyl
Under the air conditions, in a reaction tubes, add successively 4-bromofluorobenzene (175.0 mg, 1.0 mmol), phenylo boric acid (183.0 mg, 1.5 mmol), salt of wormwood (276.0 mg, 2.0 mmol), Tetrabutyl amonium bromide (322.0 mg, 1.0 mmol), catalyzer
4(0.7 mg, 0.1 mol%), water (2.0 mL) is as reaction solvent, in 100
oReaction is 2 hours in the C oil bath, and 3 mL ethyl acetate extractions are used in cooling at every turn, triplicate with behind the anhydrous sodium sulfate drying, concentrates to get crude product after organic phase merges, silicagel column separates (leacheate is sherwood oil), gets 168 mg product 4-biphenyl ethyl ketones, productive rate 98 %.
1H?NMR(CDCl
3,?400?MHz):?δ?10.08?(s,?1H),?7.60-7.50?(m,?4H),?7.48?(t,?
J?=7.2?Hz,?2H),?7.39?(t,?
J?=7.2?Hz,?1H),?7.17?(t,?
J?=8.8?Hz,?2H);?
13C?NMR(CDCl
3,?100?MHz):?δ?161.3,?140.3,?137.4,?128.9,?128.8,?128.7,?127.3,?127.1,?115.6;?
19F?NMR(CDCl
3,?376?MHz):?δ?-115.8.
Embodiment 9,
The preparation of 4-methoxyl biphenyl
Under the air conditions, in a reaction tubes, add successively 4-methoxyl group bromobenzene (187.0 mg, 1.0 mmol), phenylo boric acid (183.0 mg, 1.5 mmol), salt of wormwood (276.0 mg, 2.0 mmol), Tetrabutyl amonium bromide (322.0 mg, 1 mmol), catalyzer
4(0.7 mg, 0.1 mol%), water (2 mL) is as reaction solvent, in 100
oReaction is 2 hours in the C oil bath, and 3 mL ethyl acetate extractions are used in cooling at every turn, triplicate with behind the anhydrous sodium sulfate drying, concentrates to get crude product after organic phase merges, silicagel column separates (leacheate is sherwood oil), gets 175 mg product 4-biphenyl ethyl ketones, productive rate 95 %.
1H?NMR(CDCl
3,?400?MHz):?δ?7.57?(t,?
J?=8?Hz,?4H),?7.44?(t,?
J?=7.4?Hz,?2H),?7.32?(t,?
J?=7.4?Hz,?2H),?7.00?(d,?
J?=8.8?Hz,?2H),?3.88?(s,?3H);?
13C?NMR(CDCl
3,?100?MHz):?δ?159.2,?140.8,?133.8,?128.7,?128.2,?126.8,?126.7,?114.2,?55.4.
The preparation of phenyl thiophene
Under the air conditions, in a reaction tubes, add successively 4-bromothiophene (163.0 mg, 1 mmol), phenylo boric acid (183.0 mg, 1.5 mmol), salt of wormwood (276.0 mg, 2.0 mmol), Tetrabutyl amonium bromide (322.0 mg, 1.0 mmol), catalyzer
4(0.7 mg, 0.1 mol%), water (2.0 mL) is as reaction solvent, in 100
oReaction is 2 hours in the C oil bath, and 3 mL ethyl acetate extractions are used in cooling at every turn, triplicate with behind the anhydrous sodium sulfate drying, concentrates to get crude product after organic phase merges, silicagel column separates (leacheate is sherwood oil), gets 157 mg product 4-biphenyl ethyl ketones, productive rate 98 %.
1H?NMR(CDCl
3,?400?MHz):?δ?7.68?(d,?
J?=7.2?Hz,?2H),?7.44?(t,
?J?=7.2?Hz,?2H),?7.38-7.31?(m,?3H),?7.14?(m,?1H);?
13C?NMR(CDCl
3,?100?MHz):?δ?144.6,?134.5,?129.0,?128.1,?127.5,?126.0,?124.9,?123.2。
Embodiment 11,
The preparation of 2-methyl diphenyl
Under the air conditions, in a reaction tubes, add successively 2-bromobenzene (171.0 mg, 1.0 mmol), phenylo boric acid (183.0 mg, 1.5 mmol), salt of wormwood (276.0 mg, 2.0 mmol), Tetrabutyl amonium bromide (322.0 mg, 1 mmol), catalyzer
4(0.7 mg, 0.1 mol%), water (2 mL) is as reaction solvent, in 100
oReaction is 2 hours in the C oil bath, and 3 mL ethyl acetate extractions are used in cooling at every turn, triplicate with behind the anhydrous sodium sulfate drying, concentrates to get crude product after organic phase merges, silicagel column separates (leacheate is sherwood oil), gets 160 mg product 4-biphenyl ethyl ketones, productive rate 95 %.
1H?NMR(CDCl
3,?400?MHz):?δ?7.59-7.51?(m,?2H),?7.50-7.49?(m,?3H),?7.44-7.40?(m,?4H),?2.45?(s,?3H);?
13C?NMR?(CDCl
3,?100?MHz):?δ?142.1,?142.1,?135.5,?130.5,?123.0,?129.4,?128.2,?127.4,?127.3,?126.9,?125.9,?20.6。
Embodiment 12,
The preparation of the Pd nano particle of pH response
Under the air conditions, in a reaction tubes, add successively 4-bromoacetophenone (199.0 mg, 1.0 mmol), phenylo boric acid (183.0 mg, 1.5 mmol), salt of wormwood (276.0 mg, 2.0 mmol), catalyzer
4(0.7 mg, 0.1 mol%), water (2.0 mL) is as reaction solvent, in 100
oReaction is 2 hours in the C oil bath, and 3 mL extracted with diethyl ether are used in cooling at every turn, triplicate, add 5 mL ethanol to aqueous phase, have gray solid to separate out, centrifugal after, pour out clear liquid, again add the mixed solvent washing of second alcohol and water 1:1, centrifugal, repeat 3 times after, the solid residue ultra-sonic dispersion in ethanol, is dripped sample to the copper mesh that is used for transmission electron microscope.The transmission electron microscope picture shows the generation of Pd nano particle.Fig. 1.
Embodiment 13,
With the palladium N-heterocycle carbine inner complex of pH response recycling as the catalyst system of catalyzer
Under the air conditions, in a reaction tubes, add successively 4-bromoacetophenone (199.0 mg, 1.0 mmol), phenylo boric acid (183.0 mg, 1.5 mmol), salt of wormwood (276.0 mg, 2.0 mmol), catalyzer
4(0.7 mg, 0.1 mol%), water (2.0 mL) is as reaction solvent, in 100
oReaction is 2 hours in the C oil bath, cooling is used 3 mL extracted with diethyl ether, triplicate at every turn, organic phase merges rear with behind the anhydrous sodium sulfate drying, concentrate to get crude product, silicagel column separates (leacheate is sherwood oil), gets product 4-biphenyl ethyl ketone, water continues to add the 4-bromoacetophenone, phenylo boric acid, salt of wormwood and water carry out the next round reaction, repeat 4 according to above-mentioned steps and take turns.Fig. 2 a.
Embodiment 14,
With the palladium N-heterocycle carbine inner complex of pH response recycling as the catalyst system of catalyzer
Under the air conditions, in a reaction tubes, add successively 4-bromoacetophenone (199.0 mg, 1.0 mmol), phenylo boric acid (183.0 mg, 1.5 mmol), salt of wormwood (276.0 mg, 2.0 mmol), catalyzer
4(0.7 mg, 0.1 mol%), water (2.0 mL) is as reaction solvent, in 100
oReaction is 2 hours in the C oil bath, and 3 mL extracted with diethyl ether are used in cooling at every turn, triplicate with behind the anhydrous sodium sulfate drying, concentrates to get crude product after organic phase merges, silicagel column separates (leacheate is sherwood oil), gets product 4-biphenyl ethyl ketone, water with the hcl acidifying of 2mol/L to pH be 4, after centrifugal with whizzer, pour out supernatant liquid, continue to add 4-bromoacetophenone, phenylo boric acid, salt of wormwood and water carry out the next round reaction, repeat 4 according to above-mentioned steps and take turns.Fig. 2 b.
Embodiment 15,
The N-heterocycle carbine inner complex pH responding ability of the palladium of pH response
The N-heterocycle carbine inner complex of palladium is under alkaline condition when (pH〉8.0), and is water-soluble, is acidified to acidic conditions (pH＜5.0) with dilute hydrochloric acid and precipitates, and has the pH response function.Fig. 3
Embodiment 16,
The pH responding ability of palladium N-heterocycle carbine inner complex in catalytic applications of pH response
Under the air conditions, in a reaction tubes, add successively 4-bromoacetophenone (199.0 mg, 1.0 mmol), phenylo boric acid (183.0 mg, 1.5 mmol), salt of wormwood (276.0 mg, 2.0 mmol), catalyzer
4(0.7 mg, 0.1 mol%), water (2.0 mL) is as reaction solvent, in 100
oReaction is 2 hours in the C oil bath, and 3 mL extracted with diethyl ether are used in cooling at every turn, triplicate, water with the hcl acidifying of 2mol/L to pH be 4, leave standstill, catalyst precipitation is got off.Fig. 4.
Claims (9)
1. the palladium N-heterocycle carbine inner complex of pH response, be used for the catalyzer at the cross-coupling reaction of pure water medium aryl halide, it is characterized in that two N-heterocycle carbine compounds take the acid functionalization of 4-substituted benzoyl as part, two halogen atoms of the former sub-connection of palladium or Pyridine Molecules, its molecular formula is:
。
2. according to the palladium N-heterocycle carbine inner complex of pH response claimed in claim 1, it is characterized in that described palladium by two chlorine Atomic coordinates, its molecular formula is:
。
3. according to the palladium N-heterocycle carbine inner complex of pH response claimed in claim 1, it is characterized in that described palladium by two bromine coordinations, its molecular formula is:
4. according to the palladium N-heterocycle carbine inner complex of pH response claimed in claim 1, it is characterized in that described palladium by a chlorine atom and a bromine atoms coordination, its molecular formula is:
。
5. according to the palladium N-heterocycle carbine inner complex of pH response claimed in claim 1, it is characterized in that described palladium connects two Pyridine Molecules, its molecular formula is:
6. the preparation method of the palladium N-heterocycle carbine inner complex of a pH claimed in claim 1 response, it is characterized in that: take methyl-sulphoxide as solvent, the acid chloride and the two imidazol ion salt of the dibromo that contains benzoic ether that add mol ratio 1:1,60 degrees centigrade of stirrings are warming up to 130 degrees centigrade and continue reaction 2 hours after 12 hours, concentrated, with tetrahydrofuran (THF) washing 3 times, vacuum-drying obtains palladium N-heterocycle carbine inner complex; In the solvent of first alcohol and water, after the hydrolysis of adding lithium hydroxide, add hydrochloric acid or Hydrogen bromide acidifying, wash solid with water the final vacuum drying, obtain the palladium N-heterocycle carbine inner complex of pH response.
7. the pH responding ability of the palladium N-heterocycle carbine inner complex of a pH claimed in claim 1 response, it is characterized in that: the N-heterocycle carbine inner complex of palladium is under alkaline condition when (pH〉8.0), water-soluble, being acidified to acidic conditions (pH＜5.0) with dilute hydrochloric acid precipitates, have the pH response function, this process is reversible.
8. the purposes of the palladium N-heterocycle carbine inner complex of each described pH response of a claim 1-7, it is characterized in that: the N-heterocycle carbine inner complex of the palladium of pH response can be as the catalyzer of halogenated aryl hydrocarbon in the water and aryl boric acid cross-coupling reaction; Because reaction is carried out under alkaline condition, catalyzer is water-soluble, acid adding after the reaction, and catalyst precipitation is got off, and through behind the simple filtration drying, namely can be used for the catalyzed reaction of next round; Whole catalyst system is easy to Separation and Recovery and can be repeatedly recycled.
9. the Pd nano particle that generates in the cross-coupling reaction process of the palladium N-heterocycle carbine inner complex of pH claimed in claim 1 response aryl halide and aryl boric acid in water medium, the N-heterocyclic carbene ligand is used as the stablizer of nanoparticle.
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| CN105348327A (en) * | 2015-12-14 | 2016-02-24 | 山东师范大学 | Organic ligand and Pd/Pb-based bi-metal organic framework as well as synthetic method and application thereof |
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| Title |
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| LIUYI LI等，: "pH-Responsive chelating N-heterocyclic dicarbene palladium(II) complexes:recoverable precatalysts for Suzuki–Miyaura reaction in pure water", 《GREEN CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105348327A (en) * | 2015-12-14 | 2016-02-24 | 山东师范大学 | Organic ligand and Pd/Pb-based bi-metal organic framework as well as synthetic method and application thereof |
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