CN103242372A - Benzo-quinoline triphenylphosphine ring iridium hydride adduct, as well as preparation method and application thereof - Google Patents
Benzo-quinoline triphenylphosphine ring iridium hydride adduct, as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a benzo-quinoline triphenylphosphine ring iridium hydride adduct. The compound has the general formula in the specification, wherein R is H,-CH3,-OCH3,-C6H5 or-CHO, and R is positioned in the position of 3, 5, 6 or 8 of benzo-quinoline. The preparation steps of the compound are as follows: taking a benzo-quinoline derivative, iridium trichloride and triphenylphosphine, adding into a solvent, performing heating reflux under gas protection, and filtering after the end of the reaction to obtain the benzo-quinoline triphenylphosphine ring iridium hydride adduct. The prepared benzo-quinoline triphenylphosphine ring iridium hydride adduct is a high-activity catalyst which can catalyze the reaction of aryl alkyne and aryl benzyl alcohol to obtain an aryl ketone compound. The benzo-quinoline triphenylphosphine ring iridium hydride adduct is taken as a metal catalyst, the using quantity of the catalyst is small, a cheap weak base is used, and then the reaction of the aryl alkyne and the aryl benzyl alcohol can be catalyzed efficiently. The method has the advantages of mild reaction conditions, wide range of reaction substrates, economy, high efficiency and the like, and further has important application values.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to a class benzoquinoline triphenylphosphine ring iridium hydrogen adducts, and the synthetic and application of this compounds.
Background technology
Aryl ketones and derivative thereof are the important structure unit of many natural products, medicine, synthetic intermediate, and Application Areas is very extensive.The classical synthetic method of aryl ketones derivative need be carried out polystep reaction usually, and with the poor compatibility of other functional groups, every kind of reaction needs with different halohydrocarbon, have defectives such as productive rate is low, catalyst levels is big.Compare with halohydrocarbon, alcohol extensively exists, and is relatively cheap, nontoxic, higher Atom economy arranged, and the by product of reaction is water, environmentally friendly.In recent years, researcher utilizes transition metal-catalyzed alcohol through the automatic transfer process of hydrogen, and the research for preparing the aryl ketones derivative with the carbonyl compound direct reaction has obtained remarkable progress.Develop new synthetic method, be unable to do without high-efficiency catalytic system, the research appropriate catalyst is one of sixty-four dollar question.In the linked reaction that alcohol participates in, studying more catalyzer is metal complexs such as Ru, Ir, and the linked reaction condition is harsh, uses the catalyzer of higher dosage and excessive part.In numerous transition metal complexes, Cyclometalated compound has the preparation of being easy to, modifies, to advantages such as heat and air-stable, catalytic activity height, life-span are long, makes them play the part of very important role in organic synthesis and catalytic chemistry.
Ring iridium metals compound for catalysis has good catalytic efficiency by alcohol to the hydrogen transfer reactions of aldehyde; In the ring complex of iridium, [Ir (cod) Cl] 2(cod=1,5-cyclooctadiene) be one of the efficient of this reaction of catalysis and catalyzer of good catalytic activity, wherein [Ir (cod) Cl] 2/PPh3 ring iridium catalyst system has pretty good performance; And other ring iridic compound catalyzer that is used for this reaction is reported less.Recently our reported first ring iridium triphenyl adducts, under optimized reaction conditions, efficient catalytic alcohol is through the linked reaction (J.Organomet.Chem.2012,700,214.) of the automatic transfer process of hydrogen and carbonyl compound.Though ring iridium metals compound and ring iridium triphenylphosphine adducts thereof have a lot of reports, and encircle also rare report of iridium triphenylphosphine hydrogen adducts.So far, yet there are no ring iridium triphenylphosphine hydrogen adducts as catalyst aryl alkynes and the reaction of aryl benzylalcohol, the report of synthetic preparation aryl ketones derivative.
Summary of the invention
The object of the present invention is to provide a class benzoquinoline triphenylphosphine ring iridium hydrogen adducts, the synthetic method of this compounds also is provided simultaneously.Another object of the present invention is that the benzoquinoline triphenylphosphine ring iridium hydrogen adducts that obtains is made metal catalyst, catalyzes and synthesizes aryl ketones.
Based on above-mentioned purpose, the present invention adopts following technical scheme: benzoquinoline triphenylphosphine ring iridium hydrogen adducts has following general formula:
The preparation method of described benzoquinoline triphenylphosphine ring iridium hydrogen adducts; may further comprise the steps: get benzoquinoline derivative, iridous chloride and triphenylphosphine and join in the solvent; reflux under gas shield, reaction finishes after-filtration, namely gets benzoquinoline triphenylphosphine ring iridium hydrogen adducts.
Among the described preparation method, the mol ratio of benzoquinoline derivative and iridium black, triphenylphosphine is 1:(1-1.5): (2-5); Described solvent is that ethylene glycol monoethyl ether and water volume ratio are the mixed solvent of 3:1; Temperature of reaction is 100 ℃, and the reaction times is 8-48 hour, and described gas is nitrogen.
The purposes of described benzoquinoline triphenylphosphine ring iridium hydrogen adducts: described compound is used as metal catalyst.
Described benzoquinoline triphenylphosphine ring iridium hydrogen adducts is highly active catalyzer, utilizes the reaction of described benzoquinoline triphenylphosphine ring iridium hydrogen adducts catalysis aryl alkynes and aryl benzylalcohol, obtains aromatic ketone compound.Described reaction mechanism is:
The general formula of described aryl ketones is:
The synthesis step of described aryl ketones is: benzoquinoline triphenylphosphine ring iridium hydrogen adducts, aryl alkynes, aryl benzylalcohol and alkali are joined in the solvent; reacted 10-48 hour at 80-150 ℃ under the gas shield; reaction is finished; be down to room temperature; adding water urges and going out; use dichloromethane extraction, aftertreatment gets the product aryl ketones.
In the synthesis step of described aryl ketones, described alkali is yellow soda ash, salt of wormwood, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium phosphate or potassiumphosphate; Described solvent is dioxane, benzene, toluene, tetrahydrofuran (THF) or N, dinethylformamide.
During synthesizing aryl ketone, described, the mol ratio of benzoquinoline triphenylphosphine ring iridium hydrogen adducts and aryl alkynes, aryl benzylalcohol, alkali is (0.005～0.05): 1:(1～3): (0.1～3).
In the aforesaid method, preferably, gases used is nitrogen.
The present invention synthesizes corresponding benzoquinoline derivative triphenylphosphine ring iridium hydrogen adducts by the reaction of benzoquinoline derivative, iridous chloride and triphenylphosphine.Be metal catalyst with benzoquinoline derivative triphenylphosphine ring iridium hydrogen adducts, with cheap weak base, just can efficient catalytic aryl alkynes and the reaction of aryl benzylalcohol, and catalyst levels is little, a kind of synthetic method of new practicality is provided for the preparation aryl ketones.This method has advantages such as reaction conditions gentleness, reaction substrate scope are wide, economical and efficient, has important use and is worth.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but protection scope of the present invention is not limited in this.
Embodiment 1
Benzoquinoline triphenylphosphine ring iridium hydrogen adducts has following general formula:
Embodiment 2
The preparation of benzoquinoline triphenylphosphine ring iridium hydrogen adducts (1): under the high pure nitrogen protection; in the Schlek reaction tubes of 25ml, add 1mmol benzoquinoline, 1mmol iridous chloride, 2mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml; with nitrogen replacement reaction tubes 3 times; be heated to 100 ℃ with oil bath then under magnetic agitation, reaction refluxed 8 hours.Reaction finishes after-filtration, namely gets benzoquinoline triphenylphosphine ring iridium hydrogen adducts, and productive rate is 86%.The nmr analysis data of this compound are as follows: 1HNMR: δ=8.66 (d, 1H, Py-H), 7.92 (d, 1H, Py-H), 7.75 (d, 2H, Ph-H), 7.27-7.60 (m, 34H, Ph-H) ,-16.82 (t, 1H, Ir-H).
Embodiment 3
5-methyl benzoquinoline triphenylphosphine ring iridium hydrogen adducts (2): under the high pure nitrogen protection; in the Schlek reaction tubes of 25ml, add 1mmol5-methyl benzoquinoline, 1.2mmol iridous chloride, 2.5mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml; with nitrogen replacement reaction tubes 3 times; be heated to 100 ℃ with oil bath then under magnetic agitation, reaction refluxed 10 hours.Reaction finishes after-filtration, namely gets 5-methyl benzoquinoline triphenylphosphine ring iridium hydrogen adducts, and productive rate is 89%.The nmr analysis data of this compound are as follows: 1HNMR: δ=8.62 (d, 1H, Py-H), 7.90 (d, 1H, Py-H), 7.71 (d, 1H, Ph-H), 7.23-7.58 (m, 34H, Ph-H), 2.45 (s, 3H, CH
3) ,-16.87 (t, 1H, Ir-H).
Embodiment 4
5-phenyl benzoquinoline triphenylphosphine ring iridium hydrogen adducts (4): under the high pure nitrogen protection; in the Schlek reaction tubes of 10ml, add 1mmol5-phenyl benzoquinoline, 1.5mmol iridous chloride, 5mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml; with nitrogen replacement reaction tubes 3 times; be heated to 100 ℃ with oil bath then under magnetic agitation, reaction refluxed 24 hours.Reaction finishes after-filtration, namely gets 5-phenyl benzoquinoline triphenylphosphine ring iridium hydrogen adducts, and productive rate is 85%.The nmr analysis data of this compound are as follows: 1HNMR: δ=8.98 (d, 1H, Py-H), 7.97 (d, 1H, Py-H), 7.83 (d, 1H, Ph-H), 7.28-7.64 (m, 39H, Ph-H) ,-16.91 (t, 1H, Ir-H).
Embodiment 5
3-methoxyl group benzo quinoline triphenylphosphine ring iridium hydrogen adducts (7): under rare gas element (as high-purity helium) protection; in the Schlek reaction tubes of 25ml, add 1mmol3-methoxyl group benzo quinoline, 1.3mmol iridous chloride, 2.6mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml; with nitrogen replacement reaction tubes 3 times; be heated to 100 ℃ with oil bath then under magnetic agitation, reaction refluxed 36 hours.Reaction finishes after-filtration, namely gets 3-methoxyl group benzo quinoline triphenylphosphine ring iridium hydrogen adducts, and productive rate is 90%.The nmr analysis data of this compound are as follows: 1HNMR: δ=8.75 (d, 1H, Py-H), 8.31 (d, 1H, Ph-H), 7.76 (d, 1H, Ph-H), 7.20-7.53 (m, 33H, Ph-H), 6.73 (d, 1H, Ph-H), 3.76 (s, 3H, OCH
3) ,-16.95 (t, 1H, Ir-H).
Embodiment 6
3-aldehyde radical benzoquinoline triphenylphosphine ring iridium hydrogen adducts (9): under the high pure nitrogen protection; in the Schlek reaction tubes of 25ml, add 1mmol3-aldehyde radical benzoquinoline, 1.5mmol iridous chloride, 3mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml; with nitrogen replacement reaction tubes 3 times; be heated to 100 ℃ with oil bath then under magnetic agitation, reaction refluxed 48 hours.Reaction finishes after-filtration, namely gets 3-aldehyde radical benzoquinoline triphenylphosphine ring iridium hydrogen adducts, productive rate 88%.The nmr analysis data of this compound are as follows: 1HNMR: δ=9.88 (s, 1H, CHO), 8.92 (d, 1H, Py-H), 8.39 (d, 1H, Ph-H), 7.87 (d, 1H, Ph-H), 7.27-7.69 (m, 33H, Ph-H), 6.86 (d, 1H, Ph-H) ,-17.18 (t, 1H, Ir-H).
Embodiment 7
6-methyl benzoquinoline triphenylphosphine ring iridium hydrogen adducts (10): under the high pure nitrogen protection; in the Schlek reaction tubes of 25ml, add 1mmol6-methyl benzoquinoline, 1.1mmol iridous chloride, 2.2mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml; with nitrogen replacement reaction tubes 3 times; be heated to 100 ℃ with oil bath then under magnetic agitation, reaction refluxed 30 hours.Reaction finishes after-filtration, namely gets 6-methyl benzoquinoline triphenylphosphine ring iridium hydrogen adducts, and productive rate is 86%.The nmr analysis data of this compound are as follows: 1HNMR: δ=8.60 (d, 1H, Py-H), 7.87 (d, 1H, Py-H), 7.67 (d, 1H, Ph-H), 7.18-7.55 (m, 34H, Ph-H), 2.42 (s, 3H, CH
3) ,-16.90 (t, 1H, Ir-H).
Embodiment 8
6-phenyl benzoquinoline triphenylphosphine ring iridium hydrogen adducts (12): under the high pure nitrogen protection; in the Schlek reaction tubes of 25ml, add 1mmol6-phenyl benzoquinoline, 1.3mmol iridous chloride, 2.7mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml; with nitrogen replacement reaction tubes 3 times; be heated to 100 ℃ with oil bath then under magnetic agitation, reaction refluxed 40 hours.Reaction finishes after-filtration, namely gets 6-phenyl benzoquinoline triphenylphosphine ring iridium hydrogen adducts, and productive rate is 84%.The nmr analysis data of this compound are as follows: 1HNMR: δ=1HNMR: δ=8.96 (d, 1H, Py-H), 7.94 (d, 1H, Py-H), 7.80 (d, 1H, Ph-H), 7.26-7.62 (m, 39H, Ph-H) ,-16.87 (t, 1H, Ir-H).
Embodiment 9
8-methoxyl group benzo quinoline triphenylphosphine ring iridium hydrogen adducts (15): under the high pure nitrogen protection; in the Schlek reaction tubes of 25ml, add 1mmol8-methoxyl group benzo quinoline, 1.0mmol iridous chloride, 2.0mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml; with nitrogen replacement reaction tubes 3 times; be heated to 100 ℃ with oil bath then under magnetic agitation, reaction refluxed 24 hours.Reaction finishes after-filtration, namely gets 8-methoxyl group benzo quinoline triphenylphosphine ring iridium hydrogen adducts, and productive rate is 91%.The nmr analysis data of this compound are as follows: δ=8.73 (d, 1H, Py-H), 8.30 (d, 1H, Ph-H), 7.74 (d, 1H, Ph-H), 7.18-7.51 (m, 33H, Ph-H), 6.70 (d, 1H, Ph-H), 3.75 (s, 3H, OCH
3) ,-16.93 (t, 1H, Ir-H).
Embodiment 10
8-aldehyde radical benzoquinoline triphenylphosphine ring iridium hydrogen adducts (17): under the high pure nitrogen protection; in the Schlek reaction tubes of 25ml, add 1mmol5-methyl benzoquinoline, 1.5mmol iridous chloride, 3mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml; with nitrogen replacement reaction tubes 3 times; be heated to 100 ℃ with oil bath then under magnetic agitation, reaction refluxed 48 hours.Reaction finishes after-filtration, namely gets 8-aldehyde radical benzoquinoline triphenylphosphine ring iridium hydrogen adducts, productive rate 82%.The nmr analysis data of this compound are as follows: 1HNMR: δ=9.86 (s, 1H, CHO), 8.90 (d, 1H, Py-H), 8.36 (d, 1H, Ph-H), 7.86 (d, 1H, Ph-H), 7.26-7.67 (m, 33H, Ph-H), 6.85 (d, 1H, Ph-H) ,-17.14 (t, 1H, Ir-H).
Embodiment 11
1; synthesizing of 3-phenylbenzene-1-acetone: under the high pure nitrogen protection; the tetrahydrofuran (THF) that adds 0.005mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (1), 1mmol phenylacetylene, 1mmol benzylalcohol, 0.1mmol sodium hydroxide and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; be heated to 80 ℃ with oil bath then under magnetic agitation, reaction refluxed 10 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction of 5ml three times, merge organic phase and with dry 30 minutes of anhydrous MgSO4, filtration; Filtrate concentrates with rotatory evaporator, and the residue raffinate is developping agent with the sherwood oil, separates with silica gel thin-layer chromatography, obtains straight product 1, and 3-phenylbenzene-1-acetone, productive rate are 91%.The nmr analysis data of this compound are as follows: and 1HNMR: δ=7.90-7.95 (m, 2H, Ph-H), 7.15-7.50 (m, 8H, Ph-H), 3.20-3.25 (m, 2H, CH
2), 3.00-3.05 (m, 1H, Ph-H).
Embodiment 12
Synthesizing of 1-p-methylphenyl-3-phenyl-1-acetone: under the high pure nitrogen protection; the dioxane that adds 0.01mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (3), 1mmol phenylacetylene, the xylyl alcohol of 1.5mmol, 0.5mmol potassium hydroxide and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; be heated to 100 ℃ with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction of 5ml three times, merge organic phase and with dry 30 minutes of anhydrous MgSO4, filtration; Filtrate concentrates with rotatory evaporator, and the residue raffinate is developping agent with the sherwood oil, separates with silica gel thin-layer chromatography, obtains straight product 1-p-methylphenyl-3-phenyl-1-acetone, and productive rate is 93%.The nmr analysis data of this compound are as follows: and 1HNMR: δ=7.81 (d, 2H, Ph-H), 7.15-7.30 (m, 7H, Ph-H), 3.20-3.25 (m, 2H, CH
2), 3.00-3.05 (m, 1H, Ph-H), 2.34 (s, 3H, CH
3).
Embodiment 13
Synthesizing of 1-phenyl-3 (2-bromophenyl)-1-acetone: under the high pure nitrogen protection; the toluene that adds 0.02mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (4), 1mmol2-bromobenzene acetylene, 2mmol benzylalcohol, 1.0mmol salt of wormwood and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; be heated to 110 ℃ with oil bath then under magnetic agitation, reaction refluxed 20 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction of 5ml three times, merge organic phase and with dry 30 minutes of anhydrous MgSO4, filtration; Filtrate concentrates with rotatory evaporator, and the residue raffinate is developping agent with the sherwood oil, separates with silica gel thin-layer chromatography, obtains straight product 1-phenyl-3 (2-bromophenyl)-1-acetone, productive rate 88%.The nmr analysis data of this compound are as follows: and 1HNMR: δ=7.90-7.95 (m, 2H, Ph-H), 7.55-7.00 (m, 7H, Ph-H), 3.25-3.30 (m, 2H, CH
2), 3.10-3.20 (m, 1H, CH
2).
Embodiment 14
Synthesizing of the bromophenyl of 1-p-methylphenyl-3--1-acetone: under the high pure nitrogen protection; the benzene that adds 0.015mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (6), the bromobenzene acetylene of 1mmol, the xylyl alcohol of 2.2mmol, 1.5mmol cesium carbonate and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; be heated to 90 ℃ with oil bath then under magnetic agitation, reaction refluxed 30 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction of 5ml three times, merge organic phase and with dry 30 minutes of anhydrous MgSO4, filtration; Filtrate concentrates with rotatory evaporator, and the residue raffinate is developping agent with the sherwood oil, separates with silica gel thin-layer chromatography, obtains the bromophenyl of straight product 1-p-methylphenyl-3--1-acetone, and productive rate is 90%.The nmr analysis data of this compound are as follows: and 1HNMR: δ=7.84 (d, 2H, Ph-H), 7.15-7.25 (m, 6H, Ph-H), 3.20-3.25 (m, 2H, CH
2), 3.00-3.05 (m, 2H, CH
2), 2.40 (s, 3H, CH
3).
Embodiment 15
Synthesizing of 1-phenyl-3-p-methoxyphenyl-1-acetone: under the high pure nitrogen protection; the dioxane that adds 0.025mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (9), 1mmol phenylacetylene, 2.3mmol benzylalcohol, 2.8mmol potassiumphosphate and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; be heated to 110 ℃ with oil bath then under magnetic agitation, reaction refluxed 36 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction of 5ml three times, merge organic phase and with dry 30 minutes of anhydrous MgSO4, filtration; Filtrate concentrates with rotatory evaporator, and the residue raffinate is developping agent with the sherwood oil, separates with silica gel thin-layer chromatography, obtains straight product 1-phenyl-3-p-methoxyphenyl-1-acetone, and productive rate is 87%.The nmr analysis data of this compound are as follows: 1HNMR: δ=7.94-7.96 (m, 2H, Ph-H), 7.55 (t, 1H, Ph-H), 7.45 (t, 2H, Ph-H), 7.17 (d, 2H, Ph-H), 6.84 (d, 2H, Ph-H), 3.78 (s, 3H, CH
3), 3.26 (t, 2H, CH
2), 3.01 (t, 2H, CH
2).
Embodiment 16
Synthesizing of 1-rubigan-3-p-methoxyphenyl-1-acetone: under the high pure nitrogen protection; the toluene that adds 0.022mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (11), the chlorobenzene acetylene of 1mmol, 1.6mmol p-methoxybenzyl alcohol, 1.8mmol sodium phosphate and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; be heated to 110 ℃ with oil bath then under magnetic agitation, reaction refluxed 40 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction of 5ml three times, merge organic phase and with dry 30 minutes of anhydrous MgSO4, filtration; Filtrate concentrates with rotatory evaporator, and the residue raffinate is developping agent with the sherwood oil, separates with silica gel thin-layer chromatography, obtains straight product 1-rubigan-3-p-methoxyphenyl-1-acetone, and productive rate is 91%.The nmr analysis data of this compound are as follows: 1HNMR: δ=7.87 (d, 2H, Ph-H), 7.26 (d, 2H, Ph-H), 7.18 (d, 2H, Ph-H), 6.91 (d, 2H, Ph-H), 3.77 (s, 3H, CH
3), 3.20-3.25 (m, 2H, CH
2), 2.95-3.00 (m, 2H, CH
2).
Embodiment 17
Synthesizing of the acetylphenyl of 1--3-p-methylphenyl-1-acetone: under the high pure nitrogen protection; the benzene that adds 0.04mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (13), the acetylbenzene acetylene of 1mmol, the xylyl alcohol of 2.2mmol, 2.6mmol potassium hydroxide and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; be heated to 110 ℃ with oil bath then under magnetic agitation, reaction refluxed 32 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction of 5ml three times, merge organic phase and with dry 30 minutes of anhydrous MgSO4, filtration; Filtrate concentrates with rotatory evaporator, and the residue raffinate is developping agent with the sherwood oil, separates with silica gel thin-layer chromatography, obtains the acetylphenyl of straight product 1--3-p-methylphenyl-1-acetone, and productive rate is 86%.The nmr analysis data of this compound are as follows: 1HNMR: δ=7.93 (d, 2H, Ph-H), 7.33 (d, 2H, Ph-H), 7.27 (d, 2H, Ph-H), 6.95 (d, 2H, Ph-H), 3.21-3.27 (m, 2H, CH
2), 2.98-3.01 (m, 2H, CH
2), 2.75 (s, 3H, CH
3), 2.36 (s, 3H, CH
3).
Embodiment 18
Synthesizing of 1-naphthyl-3-phenyl-1-acetone: under the high pure nitrogen protection; the tetrahydrofuran (THF) that adds 0.03mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (15), 1mmol naphthalene acetylene, 2.6mmol benzylalcohol, 1.2mmol yellow soda ash and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; be heated to 80 ℃ with oil bath then under magnetic agitation, reaction refluxed 32 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction of 5ml three times, merge organic phase and with dry 30 minutes of anhydrous MgSO4, filtration; Filtrate concentrates with rotatory evaporator, and the residue raffinate is developping agent with the sherwood oil, separates with silica gel thin-layer chromatography, obtains straight product 1-naphthyl-3-phenyl-1-acetone, and productive rate is 92%.The nmr analysis data of this compound are as follows: and 1HNMR: δ=8.40 (s, 1H, Ph-H), 7.80-8.00 (m, 4H, Ph-H), 7.45-7.55 (m, 2H, Ph-H), 7.15-7.30 (m, 5H, Ph-H), 3.35-3.40 (m, 2H, CH
2), 3.05-3.15 (m, 2H, CH
2).
Embodiment 19
Synthesizing of 1-ferrocenyl-3-phenyl-1-acetone: under the high pure nitrogen protection; the dioxane that adds 0.02mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (16), 1mmol phenylacetylene, 2.3mmol ferrocene methanol, 0.8mmol sodium hydroxide and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; be heated to 110 ℃ with oil bath then under magnetic agitation, reaction refluxed 36 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction of 5ml three times, merge organic phase and with dry 30 minutes of anhydrous MgSO4, filtration; Filtrate concentrates with rotatory evaporator, and the residue raffinate is developping agent with the sherwood oil, separates with silica gel thin-layer chromatography, obtains straight product 1-ferrocenyl-3-phenyl-1-acetone, and productive rate is 96%.The nmr analysis data of this compound are as follows: and 1HNMR: δ=7.20-7.35 (m, 5H, Ph-H), 4.75 (s, 2H, C
5H
4), 4.45 (s, 2H, C
5H
4), 4.07 (s, 5H, C
5H
5), 3.00-3.10 (m, 4H, CH
2).
Embodiment 20
Synthesizing of 1-p-methylphenyl-3-ferrocenyl-1-acetone: under the high pure nitrogen protection; the N that adds 0.05mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (17), 1mmol ferrocenyl acetylene, the xylyl alcohol of 3mmol, 3mmol potassium hydroxide and 3ml in the Schlek reaction tubes of 10ml; dinethylformamide; with nitrogen replacement reaction tubes 3 times; be heated to 150 ℃ with oil bath then under magnetic agitation, reaction refluxed 48 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction of 5ml three times, merge organic phase and with dry 30 minutes of anhydrous MgSO4, filtration; Filtrate concentrates with rotatory evaporator, and the residue raffinate is developping agent with the sherwood oil, separates with silica gel thin-layer chromatography, obtains straight product 1-p-methylphenyl-3-ferrocenyl-1-acetone, and productive rate is 94%.The nmr analysis data of this compound are as follows: 1HNMR: δ=7.86 (d, 2H, Ph-H), 7.15 (d, 2H, Ph-H), 4.71 (s, 2H, C
5H
4), 4.40 (s, 2H, C
5H
4), 4.02 (s, 5H, C
5H
5), 3.03-3.08 (m, 4H, CH
2), 2.42 (s, 3H, CH
3).
Claims (8)
1. benzoquinoline triphenylphosphine ring iridium hydrogen adducts is characterized in that this compound has following general formula:
2. the preparation method of the described benzoquinoline triphenylphosphine of claim 1 ring iridium hydrogen adducts; it is characterized in that; may further comprise the steps: get benzoquinoline derivative, iridous chloride and triphenylphosphine and join in the solvent; reflux under gas shield; reaction finishes after-filtration, namely gets benzoquinoline triphenylphosphine ring iridium hydrogen adducts.
3. as the preparation method of benzoquinoline triphenylphosphine ring iridium hydrogen adducts as described in the claim 2, it is characterized in that the mol ratio of benzoquinoline derivative and iridium black, triphenylphosphine is 1 ︰ (1-1.5) ︰ (2-5); Described solvent is that ethylene glycol monoethyl ether and water volume ratio are the mixed solvent of 3 ︰ 1; Described gas is nitrogen; Reaction times is 8-48 hour.
4. the purposes of the described benzoquinoline triphenylphosphine of claim 1 ring iridium hydrogen adducts is characterized in that, described compound is used as metal catalyst.
5. as the purposes of benzoquinoline triphenylphosphine ring iridium hydrogen adducts as described in the claim 4, it is characterized in that, utilize the reaction of described benzoquinoline triphenylphosphine ring iridium hydrogen adducts catalysis aryl alkynes and aryl benzylalcohol, obtain aromatic ketone compound, the general formula of described aryl ketones is:
Wherein
, R is-H ,-CH
3,-C
2H
5,-C
3H
7,-Cl ,-Br ,-F ,-CN ,-NO
2,-CHO ,-OCH
3Or-COCH
3, R is positioned at arbitrary position on the aromatic ring.
6. as the purposes of benzoquinoline triphenylphosphine ring iridium hydrogen adducts as described in the claim 5; it is characterized in that; the synthesis step of described aryl ketones is: benzoquinoline triphenylphosphine ring iridium hydrogen adducts, aryl alkynes, aryl benzylalcohol and alkali are joined in the solvent; under gas shield, reacted 10-48 hour at 80-150 ℃; reaction is finished, and is down to room temperature, adds water and urges and going out; use dichloromethane extraction, aftertreatment gets the product aryl ketones.
7. as the purposes of benzoquinoline triphenylphosphine ring iridium hydrogen adducts as described in the claim 6, it is characterized in that described alkali is yellow soda ash, salt of wormwood, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium phosphate or potassiumphosphate; Described solvent is dioxane, benzene, toluene, tetrahydrofuran (THF) or N, dinethylformamide; Described gas is nitrogen.
8. as the purposes of benzoquinoline triphenylphosphine ring iridium hydrogen adducts as described in claim 6 or 7, it is characterized in that the mol ratio of described benzoquinoline triphenylphosphine ring iridium hydrogen adducts and aryl alkynes, aryl benzylalcohol, alkali is (0.005～0.05) ︰, 1 ︰ (1～3) ︰ (0.1～3).
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| CN104356170A (en) * | 2014-10-27 | 2015-02-18 | 洛阳师范学院 | Ruthenium iridium heteronuclear ring metal compound, and preparation method and application thereof |
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| CN114958274A (en) * | 2022-06-28 | 2022-08-30 | 韦尔通(厦门)科技股份有限公司 | Carbon dioxide carbonyl reaction type polyurethane hot melt adhesive and preparation method thereof |
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