CN109651160A - A method of catalysis phenylacetylene hydroamination reaction prepares olefinic amine compound - Google Patents
A method of catalysis phenylacetylene hydroamination reaction prepares olefinic amine compound Download PDFInfo
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- CN109651160A CN109651160A CN201910072457.6A CN201910072457A CN109651160A CN 109651160 A CN109651160 A CN 109651160A CN 201910072457 A CN201910072457 A CN 201910072457A CN 109651160 A CN109651160 A CN 109651160A
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- phenylacetylene
- amine compound
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- hydroamination reaction
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
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Abstract
The present invention provides a kind of methods that catalysis phenylacetylene hydroamination reaction prepares olefinic amine compound, it is characterized in that, it include: using phenylacetylene and secondary amine as raw material, by it under nickelous imine composition catalyst action, hydroamination reaction occurs in a solvent, it is post-treated again after reaction, obtain eneamines product；Wherein: the nickelous imine composition catalyst molecule formula is [R1R2C(C5H4N)2] Ni=NPh, R1And R2Independently selected from H, CH3And Ph, aromatic hydrocarbon are solvent.Catalyst of the present invention has high catalytic activity and regioselectivity, and synthesis technology is simply green, has excellent selectivity and high yield, and Atom economy is high, reduces the three wastes and generates, environmental-friendly, easy to operate, is suitble to industrialized production.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, and in particular to the nickelous imine composition containing pyridine ligand is catalyzed benzene
The method that acetylene hydroamination reaction prepares olefinic amine compound.
Background technique
Enamine compound plays an important role in multiple fields, is such as suitable for various nitrogen-containing heterocycles as presoma and spreads out
The synthesis of biology；Its own also has special pharmacological property, is present in numerous natural products and drug as key structural elements；This
Outer enamine is widely used in the preparation of Chiral Amine as intermediate.The method of conventional construction enamine mainly has condensation anti-
Answer, addition reaction, heterocycle cracking and imines prepare the several methods such as enamine and some special synthetic method such as Curtius reset,
Amide α, β elimination reaction and ketoxime reductive acylation etc.；These methods have clearly disadvantageous: (1) reaction condition is more demanding,
Such as high temperature and pressure or extremely low temperature；(2) low to the tolerance of reaction raw materials different functionalities group；(3) amino agents type has
Limit；(4) reaction system is required high, such as absolute anaerobic, catalyst type be few and dosage is high, particular ligand；(5) it reacts
Raw material it is restricted, such as type of feed it is single, prepare cumbersome difficulty.These deficiencies significantly limit the hair of enamine chemistry
Exhibition.And enamine is prepared by the hydroamination reaction of alkynes more simple, reaction condition milder, and reaction of atomic economy is high
(100%), therefore the hydroamination reaction of alkynes is the best practice for synthesizing high value olefinic amine compound.
Summary of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to propose a kind of catalysis phenylacetylene hydroamination reaction system
The method of standby olefinic amine compound.
Technical solution of the present invention is specifically described as follows:
The present invention provides a kind of nickelous imine composition [Ni] catalysis phenylacetylene hydroamination reaction system containing pyridine ligand
The method of standby olefinic amine compound, specific reaction are as follows:
Technical solution of the present invention is specifically described as follows:
A method of catalysis phenylacetylene hydroamination reaction prepares olefinic amine compound characterized by comprising with benzene second
Alkynes and secondary amine are that hydroamination reaction occurs in a solvent for raw material, instead by it under nickelous imine composition catalyst action
It is post-treated again after answering, obtain eneamines product；Wherein: the nickelous imine composition catalyst molecule formula is
[R1R2C(C5H4N)2] Ni=NPh, R1And R2Independently selected from H, CH3And Ph, aromatic hydrocarbon are solvent.
Preferably, the molar ratio of the catalyst and phenylacetylene is 1000:1~500:1.
Preferably, the molar ratio of the phenylacetylene and secondary amine is 1.5:1~1.0:1.
Preferably, the solvent is toluene；The ratio of solvent and phenylacetylene is 1.:1~20:1mL/g.
Preferably, the hydroamination reaction temperature is 60~100 DEG C.
Preferably, the hydroamination reaction time is 6~12h.
Preferably, the secondary amine is the secondary amine that methyl, ethyl, isopropyl or phenyl replace.
Preferably, the step of post-processing includes: and ethyl acetate is added after reaction to be extracted, and liquid separation is organic
It is mutually dried with anhydrous sodium sulfate, refilters concentration, purified through recrystallization or column chromatography scheme, obtained final eneamines and produce
Object.
It is highly preferred that the extraction times can be 2-4 times, preferably 3 times.
Compared to the prior art, the beneficial effects of the present invention are:
(1) catalyst nickelous imine composition and physical and chemical stability with higher and thermostabilization in the present invention
Property, it keeps in air or still stablizing under high temperature；Therefore harsh conditions such as anhydrous and oxygen-free environment is not needed in reaction process.
(2) Atom economy of phenylacetylene hydroamination reaction of the invention is 100%, and theoretically the reaction is without any by-product
Object avoids the generation of a large amount of waste residues, has the characteristics of environmentally protective, economical and efficient.
(3) phenylacetylene hydroamination reaction catalysis work i.e. with higher under conditions of mild (60-100 DEG C) in the present invention
Property, high income (87%~96%), and regioselectivity is good, is anti-Markovnikov addition product.
(4) catalyst activity that uses of the present invention is high, can high yield and it is highly selective obtain exclusive product, can urge
Change substrate kind is more, and universality is good, and raw material is simple and easy to get, and reaction condition is mild, high catalytic efficiency, and Atom economy is high, at
This lower and product is easily isolated, and will not generate a large amount of waste residues, is suitble to industrialized production.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of catalyst nickelous imine composition in embodiment 1,4,5,6.
Fig. 2 is the infrared spectrogram of catalyst nickelous imine composition in embodiment 2.
Fig. 3 is the infrared spectrogram of catalyst nickelous imine composition in embodiment 3.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
The molecular formula of nickelous imine composition catalyst described in following embodiment is [R1R2C(C5H4N)2] Ni=NPh,
Structural formula is (I), R1And R2Independently selected from H, CH3And Ph.The catalyst is commercially available customed product.
Embodiment 1: nickelous imine composition catalysis phenylacetylene hydroamination reaction prepares enamine
By catalyst [CH2(C5H4N)2] Ni=NPh (3.2mg, 0.00001mol), phenylacetylene (1.02g, 0.01mol) and
Reaction tube is added in aminomethyl phenyl amine (1.02g, 0.01mol) and 5mL toluene, using phenylacetylene and aminomethyl phenyl amine as raw material, by it
Under nickelous imine composition catalyst action, occur hydroamination reaction in solvent toluene, 60 DEG C of reaction temperature, when reaction
Between be 8h, after be extracted with ethyl acetate system 3 times, liquid separation, organic phase is dried with anhydrous sodium sulfate, is refiltered dense
Contracting, concentration of reaction solution obtain corresponding eneamines through silica gel column chromatography separation (eluent is methylene chloride: ethyl acetate=5:1)
Products obtained therefrom is LC-MS and obtains product 1.9019g, yield 91% by compound.1H NMR(500MHz,CDCl3):δ7.88(d,
J=7.0Hz, 2H), 7.63-7.51 (m, 5H), 7.40-7.33 (m, 3H), 6.67 (s, 1H), 5.93 (s, 1H), 3.05 (s,
3H) .. attached drawing 1 is used catalyst [CH in embodiment 12(C5H4N)2] Ni=NPh infrared spectrogram.
Embodiment 2: nickelous imine composition catalysis phenylacetylene hydroamination reaction prepares enamine
By catalyst [(CH3)CH(C5H4N)2] Ni=NPh (3.3mg, 0.00001mol), phenylacetylene (1.22g,
Reaction tube 0.012mol) is added with Methylethyl amine (1.02g, 0.01mol) and 8mL toluene, with phenylacetylene and Methylethyl amine
Hydroamination reaction, reaction temperature occur in solvent toluene by it under nickelous imine composition catalyst action for raw material
75 DEG C, reaction time 6h, after be extracted with ethyl acetate system 3 times, liquid separation, organic phase is done with anhydrous sodium sulfate
It is dry, concentration is refiltered, concentration of reaction solution is obtained through silica gel column chromatography separation (eluent is methylene chloride: ethyl acetate=5:1)
Products obtained therefrom is LC-MS and obtains product 1.5456g, yield 96% by corresponding olefinic amine compound.1H NMR(500MHz,
CDCl3): δ 7.85 (d, J=7.0Hz, 2H), 7.48-7.41 (m, 3H), 6.67 (s, 1H), 5.95 (s, 1H), 3.11 (brs,
2H), 3.05 (s, 3H), 1.83 (t, J=7.0Hz, 3H) attached drawings 2 are used catalyst [(CH in embodiment 23)CH(C5H4N)2]
The infrared spectrogram of Ni=NPh.
Embodiment 3: nickelous imine composition catalysis phenylacetylene hydroamination reaction prepares enamine
By catalyst [PhCH (C5H4N)2] Ni=NPh (4.0mg, 0.00001mol), phenylacetylene (1.53g, 0.015mol)
Reaction tube is added with isopropyl methyl amine (1.02g, 0.01mol) and 8mL toluene, is original with phenylacetylene and isopropyl methyl amine
Material, by it under nickelous imine composition catalyst action, occurs hydroamination reaction, reaction temperature 100 in solvent toluene
DEG C, reaction time 12h, after be extracted with ethyl acetate system 3 times, liquid separation, organic phase is dried with anhydrous sodium sulfate,
Concentration is refiltered, concentration of reaction solution is corresponded to through silica gel column chromatography separation (eluent is methylene chloride: ethyl acetate=5:1)
Olefinic amine compound, products obtained therefrom is done into LC-MS and obtains product 1.5225g, yield 87%.1H NMR(500MHz,CDCl3):
δ 7.87 (d, J=7.0Hz, 2H), 7.47-7.42 (m, 3H), 6.65 (s, 1H), 5.90 (s, 1H), 3.15 (brs, 1H), 3.06
(s, 3H), 1.85 (t, J=7.2Hz, 6H) attached drawings 3 are used catalyst [PhCH (C in embodiment 35H4N)2] Ni=NPh it is red
External spectrum figure.
Embodiment 4: nickelous imine composition catalysis phenylacetylene hydroamination reaction prepares enamine
By catalyst [CH2(C5H4N)2] Ni=NPh (6.4mg, 0.00002mol), phenylacetylene (1.02g, 0.01mol) and
Reaction tube is added in dimethylamine (1.02g, 0.01mol) and 5mL toluene, using phenylacetylene and dimethylamine as raw material, by it in nickelous
Under imine composition catalyst action, occur hydroamination reaction in solvent toluene, 60 DEG C of reaction temperature, reaction time 6h,
After be extracted with ethyl acetate system 3 times, liquid separation, organic phase is dried with anhydrous sodium sulfate, refilters concentration, and concentration is anti-
Liquid is answered to obtain corresponding olefinic amine compound through silica gel column chromatography separation (eluent is methylene chloride: ethyl acetate=5:1), it will
Products obtained therefrom is LC-MS and obtains product 1.3671g, yield 93%.1H NMR(500MHz,CDCl3): δ 7.85 (d, J=7.0Hz,
2H), 7.47-7.40 (m, 3H), 6.65 (s, 1H), 5.92 (s, 1H), 3.08 (s, 6H) attached drawings 1 are catalysis used in embodiment 4
Agent [CH2(C5H4N)2] Ni=NPh infrared spectrogram.
Embodiment 5: nickelous imine composition catalysis phenylacetylene hydroamination reaction prepares enamine
By catalyst [CH2(C5H4N)2] Ni=NPh (3.2mg, 0.00001mol), phenylacetylene (1.02g, 0.01mol) and
Reaction tube is added in diethylamine (1.02g, 0.01mol) and 5mL toluene, using phenylacetylene and diethylamine as raw material, by it in nickelous
Under imine composition catalyst action, occur hydroamination reaction in solvent toluene, 80 DEG C of reaction temperature, reaction time 9h,
After be extracted with ethyl acetate system 3 times, liquid separation, organic phase is dried with anhydrous sodium sulfate, refilters concentration, and concentration is anti-
Liquid is answered to obtain corresponding olefinic amine compound through silica gel column chromatography separation (eluent is methylene chloride: ethyl acetate=5:1), it will
Products obtained therefrom is LC-MS and obtains product 1.5750g, yield 90%.1H NMR(500MHz,CDCl3): δ 7.86 (d, J=7.0Hz,
2H), 7.49-7.42 (m, 3H), 6.66 (s, 1H), 5.86 (s, 1H), 3.12 (brs, 4H), 1.80 (t, J=7.2Hz, 6H) are attached
Fig. 1 is used catalyst [CH in embodiment 52(C5H4N)2] Ni=NPh infrared spectrogram.
Embodiment 6: nickelous imine composition catalysis phenylacetylene hydroamination reaction prepares enamine
By catalyst [CH2(C5H4N)2] Ni=NPh (3.2mg, 0.00001mol), phenylacetylene (1.02g, 0.01mol) and
Reaction tube is added in diphenylamine (1.02g, 0.01mol) and 5mL toluene, using phenylacetylene and diphenylamine as raw material, by it two
Under valence nickel imine composition catalyst action, occur hydroamination reaction in solvent toluene, 80 DEG C of reaction temperature, the reaction time is
10h, after be extracted with ethyl acetate system 3 times, liquid separation, organic phase is dried with anhydrous sodium sulfate, refilters concentration, dense
Contracting reaction solution obtains corresponding eneamines chemical combination through silica gel column chromatography separation (eluent is methylene chloride: ethyl acetate=5:1)
Products obtained therefrom is LC-MS and obtains product 2.4661g, yield 91% by object.1H NMR(500MHz,CDCl3): δ 7.90 (d, J=
7.0Hz,2H),7.66-7.54(m,5H),7.49-7.40(m,5H),7.36-7.28(m,3H),6.69(s,1H),5.95(s,
1H) attached drawing 1 is used catalyst [CH in embodiment 62(C5H4N)2] Ni=NPh infrared spectrogram.
Claims (9)
1. a kind of method that catalysis phenylacetylene hydroamination reaction prepares olefinic amine compound characterized by comprising
Using phenylacetylene and secondary amine as raw material, by it under nickelous imine composition catalyst action, hydrogen occurs in a solvent
Aminating reaction, it is post-treated again after reaction, obtain eneamines product；Wherein: the nickelous imine composition catalyst
Molecular formula is [R1R2C(C5H4N)2] Ni=NPh, R1And R2Independently selected from H, CH3And Ph, aromatic hydrocarbon are solvent.
2. the method that catalysis phenylacetylene hydroamination reaction prepares olefinic amine compound as described in claim 1, which is characterized in that
The molar ratio of the catalyst and phenylacetylene is 1000:1~500:1.
3. the method that catalysis phenylacetylene hydroamination reaction prepares olefinic amine compound as described in claim 1, which is characterized in that
The molar ratio of the phenylacetylene and secondary amine is 1.5:1~1.0:1.
4. the method that catalysis phenylacetylene hydroamination reaction prepares olefinic amine compound as described in claim 1, which is characterized in that
The solvent is toluene；The ratio of solvent and phenylacetylene is 1.:1~20:1mL/g.
5. the method that catalysis phenylacetylene hydroamination reaction prepares olefinic amine compound as described in claim 1, which is characterized in that
The hydroamination reaction temperature is 60~100 DEG C.
6. the method that catalysis phenylacetylene hydroamination reaction prepares olefinic amine compound as described in claim 1, which is characterized in that
The hydroamination reaction time is 6~12h.
7. the method that catalysis phenylacetylene hydroamination reaction prepares olefinic amine compound as described in claim 1, which is characterized in that
The secondary amine is the secondary amine that methyl, ethyl, isopropyl or phenyl replace.
8. the method that catalysis phenylacetylene hydroamination reaction prepares olefinic amine compound as described in claim 1, which is characterized in that
The step of post-processing include: after reaction be added ethyl acetate extracted, liquid separation, organic phase anhydrous sodium sulfate into
Row drying refilters concentration, purifies through recrystallization or column chromatography scheme, obtains final eneamines product.
9. the method that catalysis phenylacetylene hydroamination reaction prepares olefinic amine compound as claimed in claim 8, which is characterized in that
The extraction times are 2-4 times.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183331A (en) * | 2019-06-12 | 2019-08-30 | 上海应用技术大学 | A method of enamine is catalyzed and synthesized using the palladium imine composition containing pyridine ligand |
| CN111440075A (en) * | 2020-04-24 | 2020-07-24 | 安徽天择化工有限公司 | Preparation method of tetramethylethylenediamine |
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| EP1055653A2 (en) * | 1999-05-26 | 2000-11-29 | Basf Aktiengesellschaft | Process for the preparation of alkenyl compounds |
| CN102272128A (en) * | 2008-11-06 | 2011-12-07 | 弗特克斯药品有限公司 | Modulators of atp-binding cassette transporters |
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| EP1055653A2 (en) * | 1999-05-26 | 2000-11-29 | Basf Aktiengesellschaft | Process for the preparation of alkenyl compounds |
| CN102272128A (en) * | 2008-11-06 | 2011-12-07 | 弗特克斯药品有限公司 | Modulators of atp-binding cassette transporters |
Non-Patent Citations (4)
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| HUNG WAI CHEUNG ETAL: "Hydro(trispyrazolyl)borato-Ruthenium(II) Diphosphinoamino Complex-Catalyzed Addition of b-Diketones to 1-Alkynes and Anti-Markovnikov Addition of Secondary Amines to Aromatic 1-Alkynes", 《ADV. SYNTH. CATAL.》 * |
| KAZUNORI SAKAI ETAL: "Rhodium-Catalyzed anti-Markovnikov Addition of Secondary Amines to Arylacetylenes at Room Temperature", 《ORGANIC LETTERS》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183331A (en) * | 2019-06-12 | 2019-08-30 | 上海应用技术大学 | A method of enamine is catalyzed and synthesized using the palladium imine composition containing pyridine ligand |
| CN110183331B (en) * | 2019-06-12 | 2022-07-08 | 上海应用技术大学 | Method for catalytic synthesis of enamine by using palladium-imine complex containing pyridine ligand |
| CN111440075A (en) * | 2020-04-24 | 2020-07-24 | 安徽天择化工有限公司 | Preparation method of tetramethylethylenediamine |
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