CN104923299A - Ruthenium catalysts used for catalyzing acetophenone for producing alpha-phenylethanol, and preparation method thereof - Google Patents
Ruthenium catalysts used for catalyzing acetophenone for producing alpha-phenylethanol, and preparation method thereof Download PDFInfo
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- CN104923299A CN104923299A CN201510228583.8A CN201510228583A CN104923299A CN 104923299 A CN104923299 A CN 104923299A CN 201510228583 A CN201510228583 A CN 201510228583A CN 104923299 A CN104923299 A CN 104923299A
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Abstract
The invention relates to ruthenium catalysts used for catalyzing acetophenone for producing alpha-phenylethanol, and a preparation method thereof. The invention relates to the technical field of coordination chemistry, and discloses the preparation method of the ruthenium metal organic catalysts and an application of the catalysts in a reaction of catalyzing acetophenone for producing alpha-phenylethanol. The three ruthenium metal organic catalysts adopt a same ruthenium complex as a metal precursor. Ligands are respectively novel ligands H2L<1>, H2L<2> and H2L<3>. The ligands are subjected to reactions with the ruthenium metal precursor in an acetonitrile solution; filtering and filtrate concentration are carried out; and rotary evaporation is carried out, such that nitrogen heterocyclic carbene ruthenium complexes are obtained. Imine nitrogen atoms in the ligands coordinate with ruthenium, and can be easily dissociated in a reaction with a solvent in a catalyzing reaction, such that vacancies can be produced in metal centers, and a catalytic effect is enhanced. The nitrogen heterocyclic ruthenium metal complexes have clear structures, and provide a good catalytic effect in catalyzing an acetophenone hydrogen transfer reaction. The reaction conditions are mild, and post-treatment is simple. The catalysts are valuable hydrogen transfer reaction catalysts. The complexes can effectively catalyze acetophenone for producing alpha-phenylethanol.
Description
Technical field
The present invention relates to Coordinative Chemistry technical field, particularly relate to a kind of catalysis acetophenone and generate ruthenium catalyst of alpha-phenyl ethyl alcohol and preparation method thereof.
Background technology
Alpha-phenyl ethyl alcohol is compound representative in aromatic alcohol, is also a kind of important chemical products, is widely used in the industry such as medicine, spices manufacturing industry, cosmetics, food and fine chemical product.Be in harmonious proportion as being widely used in fragrance in spices manufacturing industry, and as the main component of Rose Essentielle, for the synthesis of various attar of rose, essential oil; In a lot of pharmaceutical synthesis, alpha-phenyl ethyl alcohol is important pharmaceutical intermediate, such as calms in the synthesis of medicine at brufen, and alpha-phenyl ethyl alcohol is important raw material.Prepare alpha-phenyl ethyl alcohol at present and mainly contain the multiple methods such as natural extraction, fermentable, organic synthesis.Extract from natural plant essential oils, the method raw material sources are limited, require higher to rectifying device.Microbe fermentation method is applied more at present; a large amount of patent is had to report (ZL02137575.5, US5919991, EP1158042, JP2000041655); but the expensive raw material price such as phenylalanine, fluorophenylalanine mostly adopted, therefore production cost is high, should not realize large-scale industrial and produce.Industrial production uses organic synthesis method usually.Alpha-phenyl ethyl alcohol is prepared in the reagent reduction such as general employing tetrahydro lithium, sodium borohydride or aluminium isopropoxide, but severe reaction conditions, post processing difficulty.Transition metal ruthenium is classical catalyst, and be widely used in the reactions such as catalytic oxidation, coupling, olefin metathesis, be the study hotspot of catalyst field for many years always.Use the hydrogen transfer reaction of ruthenium catalysis to have also been obtained in recent years to study widely.We develop novel nitrogen heterocyclic carbene metal ruthenium complex at synthesis, and prove that they have the activity of catalysis acetophenone hydrogen migrationization reaction.The features such as it is simple that it has synthetic method compared with hydrogen-transfer catalyst applied traditionally, and compound property is more stable, better catalytic activity, and catalytic reaction condition is gentle, and post processing is simple, environmentally friendly.
Summary of the invention
A kind of catalysis acetophenone is the object of the present invention is to provide to generate ruthenium catalyst of alpha-phenyl ethyl alcohol and preparation method thereof, acetophenone is under this complex-catalyzed effect, there is hydrogen transfer reaction, alpha-phenyl ethyl alcohol, this hydrogen migration process is in organic synthesis, fine chemistry industry or in medical industry, is all an important reaction.
The object of the invention is to be achieved through the following technical solutions:
Catalysis acetophenone generates the ruthenium catalyst of alpha-phenyl ethyl alcohol, and described catalyst comprises a kind of complex represented with Cat.:
Wherein, R is hydrogen, methyl or normal-butyl.
Catalysis acetophenone generates the ruthenium catalyst preparation method of alpha-phenyl ethyl alcohol, and described method comprises:
A. the method for complex Cat. is prepared, wherein compound H 4L
2react with three (triphenylphosphine) ruthenous chloride and generate complex Cat.;
B. the solvent reacted is acetonitrile, and reaction temperature is 50 DEG C;
The mol ratio of c. reacting is H4L
2: three (triphenylphosphine) ruthenous chloride=1:1;
D. prepare the method for compound H 4L, be wherein obtained by reacting compound H 4L by chemical compounds I and R base substituted imidazole:
Wherein, R is hydrogen, methyl or normal-butyl.
Described catalysis acetophenone generates the ruthenium catalyst preparation method of alpha-phenyl ethyl alcohol, when R base is hydrogen (H4L
1), methyl (H4L
2) or normal-butyl (H4L
3) time, the reaction time is respectively 20 hours, 12 hours, 10 hours, and chemical compounds I and R base substituted imidazole mol ratio are 1:2.
Described catalysis acetophenone generates the ruthenium catalyst preparation method of alpha-phenyl ethyl alcohol, the described method preparing chemical compounds I, wherein aniline: chloracetyl chloride: triethylamine (mol)=1:2:5;
。
Described catalysis acetophenone generates ruthenium catalyst of alpha-phenyl ethyl alcohol and preparation method thereof, and reaction temperature is 25-80 DEG C, prioritizing selection 40-60 DEG C; Take isopropyl alcohol as solvent, potassium tert-butoxide is alkali, and catalyst and substrate mol ratio are 1:500.Ru (PPh
3) Cl
2(H4L
1), Ru (PPh
3) Cl
2(H4L
2), Ru (PPh
3) Cl
2(H4L
3) complex conversion ratio is with this understanding respectively 87.21%, 92.32%, 95.64%, is selectively respectively 97.10%, 98.76%, 100%.
Advantage of the present invention and effect are:
1. three kinds of novel nitrogen heterocycle carbine ruthenium metal complexs, are all with Ru (PPh
3)
3cl
2for metal precursor, react with o-phenylenediamine, chloracetyl chloride, triethylamine, R base substituted imidazole and obtain H4L respectively
1, H4L
2, H4L
3for part.Imine nitrogen atom in part also with ruthenium coordination, and catalytic reaction moderate rain solvent action legibility from, make metal center produce room, increase catalytic effect.
2. three kinds of novel nitrogen heterocycle ruthenium metal complex structures are clear and definite, have good catalytic effect, and reaction condition are gentle to the hydrogen transfer reaction of catalysis acetophenone, and post processing is simple, is the valuable hydrogen transfer reaction catalyst of a class.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
1, there is preparation method and the reaction condition of the novel nitrogen heterocyclic carbene metal ruthenium complex of catalysis acetophenone hydrogen transfer reaction
(1) nitrogen heterocycle carbine ligand preparation
A) be dissolved in dichloromethane solution by o-phenylenediamine, triethylamine, be placed in 100ml reaction bulb, logical argon gas, stirs half an hour under ice bath; Chloracetyl chloride is dissolved in carrene, is placed in separatory funnel, dropwise add in reaction bulb.Logical argon gas after dripping, 25 DEG C of stirring in water bath 30h.Reaction terminates rear suction filtration, washed with dichloromethane, and vacuum drying obtains white powder chemical compounds I.
B) get 25ml reaction bulb, by white powder in (1), imidazoles is dissolved in acetonitrile, H4L
1: 80 DEG C of stirring and refluxing 20h, reaction end adds ether, suction filtration washed with diethylether, vacuum drying, obtains viscous brown solid; H4L
2: 80 DEG C of stirring and refluxing 12h, reaction end adds ether has yellow solid to separate out, and vacuum drying, obtains yellow powder; H4L
3: 80 DEG C of stirring and refluxing 10h, reaction end adds ether adularescent solid and separates out, and suction filtration, vacuum drying, obtains white powder.
(2) N-heterocyclic carbine metal ruthenium complex preparation
By H4L
1join in 25ml reaction bulb, add acetonitrile (dewater deoxygenation), supersonic oscillations 5min, logical argon gas, tinfoil wraps up 50 DEG C and stirs 5 hours, adds Ru (PPh
3)
3cl
2, logical argon gas, 50 DEG C of reaction 20h, filter under argon shield, filtrate revolving steams to obtain blackish green powder Ru (PPh
3) Cl
2(H4L
1).
Ru (PPh
3) Cl
2(H4L
2), Ru (PPh
3) Cl
2(H4L
3) preparation method of complex is the same.Unlike, wherein Ru (PPh
3) Cl
2(H4L
2) need backflow 12h, Ru (PPh
3) Cl
2(H4L
3) need the 10h that refluxes.
2. three kinds of metal complex catalyzed acetophenone hydrogen transfer reactions of novel nitrogen heterocycle carbine ruthenium.
3. three kinds of novel complex catalyst pair have carried out active testing, by optimizing the parameters such as temperature, reaction time, catalyst amount, alkali consumption, impact during acetophenone hydrogen transfer reaction metal complex catalyzed on N-heterocyclic carbine ruthenium is studied, and result shows complex Ru (PPh
3) Cl
2(H4L
3) catalytic activity the highest, be oxidant at potassium tert-butoxide, catalyst and substrate are than being 1:500, and solvent is isopropyl alcohol, and reaction temperature is under 60 DEG C of reaction conditions, and catalytic conversion rate reaches 95.64%, selective close to 100%.
Claims (4)
1. catalysis acetophenone generates the ruthenium catalyst of alpha-phenyl ethyl alcohol, and it is characterized in that, described catalyst comprises a kind of complex represented with Cat.:
Wherein, R is hydrogen, methyl or normal-butyl;
Catalysis acetophenone generates the ruthenium catalyst preparation method of alpha-phenyl ethyl alcohol, and it is characterized in that, described method comprises:
A. the method for complex Cat. is prepared, wherein compound H 4L
2react with three (triphenylphosphine) ruthenous chloride and generate complex Cat.;
B. the solvent reacted is acetonitrile, and reaction temperature is 50 DEG C;
The mol ratio of c. reacting is H4L
2: three (triphenylphosphine) ruthenous chloride=1:1;
D. prepare the method for compound H 4L, be wherein obtained by reacting compound H 4L by chemical compounds I and R base substituted imidazole:
Wherein, R is hydrogen, methyl or normal-butyl.
2. catalysis acetophenone according to claim 2 generates the ruthenium catalyst preparation method of alpha-phenyl ethyl alcohol, it is characterized in that, when R base is hydrogen (H4L
1), methyl (H4L
2) or normal-butyl (H4L
3) time, the reaction time is respectively 20 hours, 12 hours, 10 hours, and chemical compounds I and R base substituted imidazole mol ratio are 1:2.
3. catalysis acetophenone according to claim 2 generates the ruthenium catalyst preparation method of alpha-phenyl ethyl alcohol, it is characterized in that, the described method preparing chemical compounds I, wherein aniline: chloracetyl chloride: triethylamine (mol)=1:2:5;
。
4. catalysis acetophenone according to claim 2 generates ruthenium catalyst of alpha-phenyl ethyl alcohol and preparation method thereof, and it is characterized in that, reaction temperature is 25-80 DEG C, prioritizing selection 40-60 DEG C; Take isopropyl alcohol as solvent, potassium tert-butoxide is alkali, and catalyst and substrate mol ratio are 1:500; Ru (PPh
3) Cl
2(H4L
1), Ru (PPh
3) Cl
2(H4L
2), Ru (PPh
3) Cl
2(H4L
3) complex conversion ratio is with this understanding respectively 87.21%, 92.32%, 95.64%, is selectively respectively 97.10%, 98.76%, 100%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867702A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of double-core palladium/ruthenium complex and its preparation and application |
| CN110002961A (en) * | 2019-04-01 | 2019-07-12 | 三峡大学 | A method of removing racemization synthesis of chiral alcohol |
| CN110694689A (en) * | 2019-10-08 | 2020-01-17 | 华东师范大学 | Polyion liquid supported ruthenium carbene complex catalyst, preparation method and application thereof |
| CN111269147A (en) * | 2020-01-14 | 2020-06-12 | 浙江工业大学 | Chiral phosphine nitrogen phosphine ligand and chiral metal organic coordination complex and application thereof |
| CN113651679A (en) * | 2021-07-20 | 2021-11-16 | 复旦大学 | Method for preparing beta-substituted ketone/alcohol by high-selectivity catalytic dehydrogenation coupling of secondary alcohol |
| CN115583865A (en) * | 2022-09-29 | 2023-01-10 | 哈尔滨工业大学（深圳） | Continuous preparation method of chiral phenethyl alcohol |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867702A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of double-core palladium/ruthenium complex and its preparation and application |
| CN109867702B (en) * | 2017-12-01 | 2021-04-13 | 中国科学院大连化学物理研究所 | Binuclear palladium/ruthenium complex and preparation and application thereof |
| CN110002961A (en) * | 2019-04-01 | 2019-07-12 | 三峡大学 | A method of removing racemization synthesis of chiral alcohol |
| CN110002961B (en) * | 2019-04-01 | 2022-05-03 | 三峡大学 | Method for racemization-free synthesis of chiral alcohol |
| CN110694689A (en) * | 2019-10-08 | 2020-01-17 | 华东师范大学 | Polyion liquid supported ruthenium carbene complex catalyst, preparation method and application thereof |
| CN111269147A (en) * | 2020-01-14 | 2020-06-12 | 浙江工业大学 | Chiral phosphine nitrogen phosphine ligand and chiral metal organic coordination complex and application thereof |
| CN113651679A (en) * | 2021-07-20 | 2021-11-16 | 复旦大学 | Method for preparing beta-substituted ketone/alcohol by high-selectivity catalytic dehydrogenation coupling of secondary alcohol |
| CN115583865A (en) * | 2022-09-29 | 2023-01-10 | 哈尔滨工业大学（深圳） | Continuous preparation method of chiral phenethyl alcohol |
| CN115583865B (en) * | 2022-09-29 | 2023-10-31 | 哈尔滨工业大学（深圳） | Continuous preparation method of chiral phenethyl alcohol |
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