CN103242372B - Benzoquinoline triphenylphosphine ring iridium hydrogen adducts and its production and use - Google Patents
Benzoquinoline triphenylphosphine ring iridium hydrogen adducts and its production and use Download PDFInfo
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- CN103242372B CN103242372B CN201310207216.0A CN201310207216A CN103242372B CN 103242372 B CN103242372 B CN 103242372B CN 201310207216 A CN201310207216 A CN 201310207216A CN 103242372 B CN103242372 B CN 103242372B
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Abstract
The invention discloses a class benzoquinoline triphenylphosphine ring iridium hydrogen adducts, this compounds has following general formula:
, wherein R is H ,-CH
3,-OCH
3,-C
6h
5or-CHO, R are positioned at the position of 3,5,6 or 8 of benzoquinoline; The preparation process of this compounds is: get benzoquinoline derivative, iridous chloride and triphenylphosphine and join in solvent, reflux under gas shield, and reaction terminates rear filtration and get final product.Obtained benzoquinoline triphenylphosphine ring iridium hydrogen adducts is highly active catalyzer, and catalysis arylalkyne and the reaction of aryl benzylalcohol, obtain aromatic ketone compound.With benzoquinoline derivative triphenylphosphine ring iridium hydrogen adducts for metal catalyst, catalyst levels is little, with cheap weak base, and just can efficient catalytic arylalkyne and the reaction of aryl benzylalcohol.The method has reaction conditions gentleness, and reaction substrate scope is wide, and the advantages such as economical and efficient, have important using value.
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 synthesis of this compounds and application.
Background technology
Aryl ketones and derivative thereof are the important feature unit of many natural products, medicine, synthetic intermediate, and Application Areas widely.The classical synthetic method of aryl ketones derivative needs to carry out polystep reaction usually, and with the poor compatibility of other functional groups, with different halohydrocarbon, the defects such as productive rate is low, catalyst levels is large need be there is in often kind of reaction.Compared with halohydrocarbon, alcohol extensively exists, relatively cheap, nontoxic, have higher Atom economy, 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 preparing aryl ketones derivative with carbonyl compound direct reaction has made great progress.Develop new synthetic method, be unable to do without efficient catalyst system, studying suitable catalyzer is one of sixty-four dollar question.In the linked reaction that alcohol participates in, studying more catalyzer is the metal complexs such as Ru, Ir, and linked reaction condition is harsher, uses the catalyzer of higher dosage and excessive part.In numerous transition metal complexes, Cyclometalated compound has and is easy to preparation, modifies, to heat and air-stable, the advantage such as catalytic activity is high, the life-span is long, makes them in organic synthesis and catalytic chemistry, play very important role.
Ring iridium metals compound for catalysis has good catalytic efficiency by alcohol to the hydrogen transfer reactions of aldehyde; In ring complex of iridium, [Ir (cod) Cl] 2(cod=1,5-cyclooctadiene) be one of the efficiency of this reaction of catalysis and the 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 for this reaction is reported less.Our reported first ring iridium triphenyl adducts recently, under the reaction conditions optimized, efficient catalytic alcohol is through the linked reaction (J.Organomet.Chem.2012,700,214.) of the automatic transfer process of hydrogen and carbonyl compound.Although ring iridium metals compound and ring iridium triphenylphosphine adducts thereof have a lot of report, and ring iridium triphenylphosphine hydrogen adducts also rare report.So far, yet there are no ring iridium triphenylphosphine hydrogen adducts as catalyst arylalkyne and the reaction of aryl benzylalcohol, the report of synthesis 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 is also provided simultaneously.Another object of the present invention is that the benzoquinoline triphenylphosphine ring iridium hydrogen adducts of acquisition 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:
wherein R is H ,-CH
3,-OCH
3,-C
6h
5or-CHO, R are positioned at the position of 3,5,6 or 8 of benzoquinoline.
The preparation method of described benzoquinoline triphenylphosphine ring iridium hydrogen adducts; comprise the following steps: get benzoquinoline derivative, iridous chloride and triphenylphosphine and join in solvent; reflux under gas shield, reaction terminates rear filtration, obtains benzoquinoline triphenylphosphine ring iridium hydrogen adducts.
In described preparation method, the mol ratio of benzoquinoline derivative and iridium black, triphenylphosphine is 1:(1-1.5): (2-5); Described solvent is ethylene glycol monoethyl ether and water volume ratio is the mixed solvent of 3:1; Temperature of reaction is 100 DEG C, 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 described benzoquinoline triphenylphosphine ring iridium hydrogen adducts catalysis arylalkyne and the reaction of aryl benzylalcohol, obtains aromatic ketone compound.Described reaction mechanism is:
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 can on aromatic ring any position.
The synthesis step of described aryl ketones is: join in solvent by benzoquinoline triphenylphosphine ring iridium hydrogen adducts, arylalkyne, aryl benzylalcohol and alkali; at 80-150 DEG C of reaction 10-48 hour under gas shield; reaction is finished; be down to room temperature; add water to urge and go out; with dichloromethane extraction, aftertreatment obtains product aryl ketones.
In the synthesis step of described aryl ketones, described alkali is sodium carbonate, salt of wormwood, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium phosphate or potassiumphosphate; Described solvent is dioxane, benzene, toluene, tetrahydrofuran (THF) or DMF.
During synthesizing aryl ketone, described in, the mol ratio of benzoquinoline triphenylphosphine ring iridium hydrogen adducts and arylalkyne, aryl benzylalcohol, alkali is (0.005 ~ 0.05): 1:(1 ~ 3): (0.1 ~ 3).
In aforesaid method, preferably, gases used is nitrogen.
The present invention goes out corresponding benzoquinoline derivative triphenylphosphine ring iridium hydrogen adducts by the Reactive Synthesis of benzoquinoline derivative, iridous chloride and triphenylphosphine.With benzoquinoline derivative triphenylphosphine ring iridium hydrogen adducts for metal catalyst, with cheap weak base, just energy efficient catalytic arylalkyne and the reaction of aryl benzylalcohol, and catalyst levels is little, for preparation aryl ketones provides a kind of synthetic method of practicality newly.The method has the advantages such as reaction conditions gentleness, reaction substrate scope are wide, economical and efficient, has important using value.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited in this.
Embodiment 1
Benzoquinoline triphenylphosphine ring iridium hydrogen adducts, has following general formula:
wherein R is H ,-CH
3,-OCH
3,-C
6h
5or-CHO, R are positioned at the position of 3,5,6 or 8 of benzoquinoline.Can be specifically:
Embodiment 2
The preparation of benzoquinoline triphenylphosphine ring iridium hydrogen adducts (1): under high pure nitrogen protection; 1mmol benzoquinoline, 1mmol iridous chloride, 2mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml is added in the Schlek reaction tubes of 25ml; with nitrogen replacement reaction tubes 3 times; then 100 DEG C are heated to oil bath under magnetic stirring, reaction backflow 8 hours.Reaction terminates rear filtration, and obtain benzoquinoline triphenylphosphine ring iridium hydrogen adducts, 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 high pure nitrogen protection; 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 is added in the Schlek reaction tubes of 25ml; with nitrogen replacement reaction tubes 3 times; then 100 DEG C are heated to oil bath under magnetic stirring, reaction backflow 10 hours.Reaction terminates rear filtration, and obtain 5-methyl benzoquinoline triphenylphosphine ring iridium hydrogen adducts, 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 high pure nitrogen protection; 1mmol5-phenyl benzoquinoline, 1.5mmol iridous chloride, 5mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml is added in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 100 DEG C are heated to oil bath under magnetic stirring, reaction backflow 24 hours.Reaction terminates rear filtration, and obtain 5-phenyl benzoquinoline triphenylphosphine ring iridium hydrogen adducts, 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 benzoquinoline triphenylphosphine ring iridium hydrogen adducts (7): under rare gas element (as high-purity helium) protection; 1mmol3-methoxyl group benzoquinoline, 1.3mmol iridous chloride, 2.6mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml is added in the Schlek reaction tubes of 25ml; with nitrogen replacement reaction tubes 3 times; then 100 DEG C are heated to oil bath under magnetic stirring, reaction backflow 36 hours.Reaction terminates rear filtration, and obtain 3-methoxyl group benzoquinoline triphenylphosphine ring iridium hydrogen adducts, 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 high pure nitrogen protection; 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 is added in the Schlek reaction tubes of 25ml; with nitrogen replacement reaction tubes 3 times; then 100 DEG C are heated to oil bath under magnetic stirring, reaction backflow 48 hours.Reaction terminates rear filtration, obtains 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 high pure nitrogen protection; 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 is added in the Schlek reaction tubes of 25ml; with nitrogen replacement reaction tubes 3 times; then 100 DEG C are heated to oil bath under magnetic stirring, reaction backflow 30 hours.Reaction terminates rear filtration, and obtain 6-methyl benzoquinoline triphenylphosphine ring iridium hydrogen adducts, 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 high pure nitrogen protection; 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 is added in the Schlek reaction tubes of 25ml; with nitrogen replacement reaction tubes 3 times; then 100 DEG C are heated to oil bath under magnetic stirring, reaction backflow 40 hours.Reaction terminates rear filtration, and obtain 6-phenyl benzoquinoline triphenylphosphine ring iridium hydrogen adducts, 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 benzoquinoline triphenylphosphine ring iridium hydrogen adducts (15): under high pure nitrogen protection; 1mmol8-methoxyl group benzoquinoline, 1.0mmol iridous chloride, 2.0mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml is added in the Schlek reaction tubes of 25ml; with nitrogen replacement reaction tubes 3 times; then 100 DEG C are heated to oil bath under magnetic stirring, reaction backflow 24 hours.Reaction terminates rear filtration, and obtain 8-methoxyl group benzoquinoline triphenylphosphine ring iridium hydrogen adducts, 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 high pure nitrogen protection; 1mmol5-methyl benzoquinoline, 1.5mmol iridous chloride, 3mmol triphenylphosphine and mixed solvent (ethylene glycol monoethyl ether and water volume ratio are 3:1) 12ml is added in the Schlek reaction tubes of 25ml; with nitrogen replacement reaction tubes 3 times; then 100 DEG C are heated to oil bath under magnetic stirring, reaction backflow 48 hours.Reaction terminates rear filtration, obtains 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; the synthesis of 3-phenylbenzene-1-acetone: under high pure nitrogen protection; the tetrahydrofuran (THF) of 0.005mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (1), 1mmol phenylacetylene, 1mmol benzylalcohol, 0.1mmol sodium hydroxide and 3ml is added in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 80 DEG C are heated to oil bath under magnetic stirring, reaction backflow 10 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase also with dry 30 minutes of anhydrous MgSO4, filter; Filtrate concentrates with rotatory evaporator, and residue raffinate take sherwood oil as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 1,3-phenylbenzene-1-acetone, productive rate is 91%.The nmr analysis data of this compound are as follows: 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
The synthesis of 1-p-methylphenyl-3-phenyl-1-acetone: under high pure nitrogen protection; 0.01mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (3), 1mmol phenylacetylene, 1.5mmol is added to the dioxane of xylyl alcohol, 0.5mmol potassium hydroxide and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 100 DEG C are heated to oil bath under magnetic stirring, reaction backflow 24 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase also with dry 30 minutes of anhydrous MgSO4, filter; Filtrate concentrates with rotatory evaporator, and residue raffinate take sherwood oil as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 1-p-methylphenyl-3-phenyl-1-acetone, productive rate is 93%.The nmr analysis data of this compound are as follows: 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
The synthesis of 1-phenyl-3 (2-bromophenyl)-1-acetone: under high pure nitrogen protection; the toluene of 0.02mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (4), 1mmol2-bromobenzene acetylene, 2mmol benzylalcohol, 1.0mmol salt of wormwood and 3ml is added in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 110 DEG C are heated to oil bath under magnetic stirring, reaction backflow 20 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase also with dry 30 minutes of anhydrous MgSO4, filter; Filtrate concentrates with rotatory evaporator, and residue raffinate take sherwood oil as developping agent, is separated, obtains straight product 1-phenyl-3 (2-bromophenyl)-1-acetone, productive rate 88% with silica gel thin-layer chromatography.The nmr analysis data of this compound are as follows: 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
1-p-methylphenyl-3-is to the synthesis of bromophenyl-1-acetone: under high pure nitrogen protection; 0.015mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (6), 1mmol is added to bromobenzene acetylene, 2.2mmol to the benzene of xylyl alcohol, 1.5mmol cesium carbonate and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 90 DEG C are heated to oil bath under magnetic stirring, reaction backflow 30 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase also with dry 30 minutes of anhydrous MgSO4, filter; Filtrate concentrates with rotatory evaporator, and residue raffinate take sherwood oil as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 1-p-methylphenyl-3-to bromophenyl-1-acetone, productive rate is 90%.The nmr analysis data of this compound are as follows: 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
The synthesis of 1-phenyl-3-p-methoxyphenyl-1-acetone: under high pure nitrogen protection; the dioxane of 0.025mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (9), 1mmol phenylacetylene, 2.3mmol benzylalcohol, 2.8mmol potassiumphosphate and 3ml is added in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 110 DEG C are heated to oil bath under magnetic stirring, reaction backflow 36 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase also with dry 30 minutes of anhydrous MgSO4, filter; Filtrate concentrates with rotatory evaporator, and residue raffinate take sherwood oil as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 1-phenyl-3-p-methoxyphenyl-1-acetone, 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
The synthesis of 1-rubigan-3-p-methoxyphenyl-1-acetone: under high pure nitrogen protection; 0.022mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (11), 1mmol is added to the toluene of chlorobenzene acetylene, 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; then 110 DEG C are heated to oil bath under magnetic stirring, reaction backflow 40 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase also with dry 30 minutes of anhydrous MgSO4, filter; Filtrate concentrates with rotatory evaporator, and residue raffinate take sherwood oil as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 1-rubigan-3-p-methoxyphenyl-1-acetone, 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
1-is to the synthesis of acetylphenyl-3-p-methylphenyl-1-acetone: under high pure nitrogen protection; 0.04mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (13), 1mmol is added to acetylbenzene acetylene, 2.2mmol to the benzene of xylyl alcohol, 2.6mmol potassium hydroxide and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 110 DEG C are heated to oil bath under magnetic stirring, reaction backflow 32 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase also with dry 30 minutes of anhydrous MgSO4, filter; Filtrate concentrates with rotatory evaporator, and residue raffinate take sherwood oil as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 1-to acetylphenyl-3-p-methylphenyl-1-acetone, 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
The synthesis of 1-naphthyl-3-phenyl-1-acetone: under high pure nitrogen protection; the tetrahydrofuran (THF) of 0.03mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (15), 1mmol naphthalene acetylene, 2.6mmol benzylalcohol, 1.2mmol sodium carbonate and 3ml is added in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 80 DEG C are heated to oil bath under magnetic stirring, reaction backflow 32 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase also with dry 30 minutes of anhydrous MgSO4, filter; Filtrate concentrates with rotatory evaporator, and residue raffinate take sherwood oil as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 1-naphthyl-3-phenyl-1-acetone, productive rate is 92%.The nmr analysis data of this compound are as follows: 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
The synthesis of 1-ferrocenyl-3-phenyl-1-acetone: under high pure nitrogen protection; the dioxane of 0.02mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (16), 1mmol phenylacetylene, 2.3mmol ferrocene methanol, 0.8mmol sodium hydroxide and 3ml is added in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 110 DEG C are heated to oil bath under magnetic stirring, reaction backflow 36 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase also with dry 30 minutes of anhydrous MgSO4, filter; Filtrate concentrates with rotatory evaporator, and residue raffinate take sherwood oil as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 1-ferrocenyl-3-phenyl-1-acetone, productive rate is 96%.The nmr analysis data of this compound are as follows: 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
The synthesis of 1-p-methylphenyl-3-ferrocenyl-1-acetone: under high pure nitrogen protection; 0.05mmol benzoquinoline triphenylphosphine ring iridium hydrogen adducts (17), 1mmol ferrocenyl acetylene, 3mmol is added to the N of xylyl alcohol, 3mmol potassium hydroxide and 3ml in the Schlek reaction tubes of 10ml; dinethylformamide; with nitrogen replacement reaction tubes 3 times; then 150 DEG C are heated to oil bath under magnetic stirring, reaction backflow 48 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase also with dry 30 minutes of anhydrous MgSO4, filter; Filtrate concentrates with rotatory evaporator, and residue raffinate take sherwood oil as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 1-p-methylphenyl-3-ferrocenyl-1-acetone, 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, it is characterized in that, this compound has following general formula:
, wherein R is H ,-CH
3,-OCH
3,-C
6h
5or-CHO, R are positioned at the position of 3,5,6 or 8 of benzoquinoline.
2. the preparation method of benzoquinoline triphenylphosphine ring iridium hydrogen adducts described in claim 1; it is characterized in that; comprise the following steps: get benzoquinoline derivative, iridous chloride and triphenylphosphine and join in solvent; reflux under gas shield; reaction terminates rear filtration, obtains benzoquinoline triphenylphosphine ring iridium hydrogen adducts.
3. the preparation method of benzoquinoline triphenylphosphine ring iridium hydrogen adducts as claimed in claim 2, is characterized in that, the mol ratio of benzoquinoline derivative and iridous chloride, triphenylphosphine is 1 ︰ (1-1.5) ︰ (2-5); The mixed solvent of described solvent to be ethylene glycol monoethyl ether and water volume ratio be 3 ︰ 1; Described gas is nitrogen; Reaction times is 8-48 hour.
4. the purposes of benzoquinoline triphenylphosphine ring iridium hydrogen adducts described in claim 1, is characterized in that, described compound is used as metal catalyst.
5. the purposes of benzoquinoline triphenylphosphine ring iridium hydrogen adducts as claimed in claim 4, it is characterized in that, utilize described benzoquinoline triphenylphosphine ring iridium hydrogen adducts catalysis aryl ethane and the reaction of aryl methyl alcohol, 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 any position on aromatic ring; Aryl in aryl ethane and aryl methyl alcohol and the Aryl in aryl ketones
1and Aryl
2identical.
6. the purposes of benzoquinoline triphenylphosphine ring iridium hydrogen adducts as claimed in claim 5; it is characterized in that; the synthesis step of described aryl ketones is: join in solvent by benzoquinoline triphenylphosphine ring iridium hydrogen adducts, aryl ethane, aryl methyl alcohol and alkali; at 80-150 DEG C of reaction 10-48 hour under gas shield; reaction is finished, and be down to room temperature, add water cancellation; with dichloromethane extraction, aftertreatment obtains product aryl ketones.
7. the purposes of benzoquinoline triphenylphosphine ring iridium hydrogen adducts as claimed in claim 6, it is characterized in that, described alkali is sodium carbonate, salt of wormwood, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium phosphate or potassiumphosphate; Described solvent is dioxane, benzene, toluene, tetrahydrofuran (THF) or DMF; Described gas is nitrogen.
8. the purposes of benzoquinoline triphenylphosphine ring iridium hydrogen adducts as claimed in claims 6 or 7, it is characterized in that, the mol ratio of described benzoquinoline triphenylphosphine ring iridium hydrogen adducts and aryl ethane, aryl methyl alcohol, alkali is (0.005 ~ 0.05) ︰ 1 ︰ (1 ~ 3) ︰ (0.1 ~ 3).
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| US20030162299A1 (en) * | 2002-02-08 | 2003-08-28 | Canon Kabushiki Kaisha | Light emissive iridium (III) complexes |
| US20080265758A1 (en) * | 2003-11-06 | 2008-10-30 | Eun-Sil Han | Organometallic complexes and organic electroluminescence device using the same |
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| US20080265758A1 (en) * | 2003-11-06 | 2008-10-30 | Eun-Sil Han | Organometallic complexes and organic electroluminescence device using the same |
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