CN106699628A - Method for preparing pyrrolidone by using levulinic acid - Google Patents
Method for preparing pyrrolidone by using levulinic acid Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
Abstract
The invention relates to a method for preparing pyrrolidone by using levulinic acid, belonging to the technical field of chemical intermediate production methods. According to the method, the levulinic acid is converted into N-substituted-5-methyl pyrrolidone in presence of a semi-sandwich iridium catalyst by taking amines as raw materials in a formic acid buffer solution system at the temperature of 50-220 DEG C. According to the technical scheme, the levulinic acid is converted into the N-substituted-5-methyl pyrrolidone by taking the semi-sandwich iridium catalyst as a catalyst at lower temperature in the formic acid buffer solution system; a product is convenient to separate and high in yield, and has a higher application value; the method is simple in technology and wide in market prospect.
Description
Technical field
The present invention relates to a kind of method that utilization levulic acid prepares pyrrolidones, belong to chemical intermediate production method skill
Art field.
Background technology
A large amount of with fossil resource use, and environmental pollution, greenhouse effects, haze problem have been on the rise.Therefore, may be used
Regenerated resources are converted into bulk chemical and automotive fuel, and reduce has important meaning to the dependence of the resources such as oil, coal
Justice.European chemistry association（EChA）By the conscientious consideration N- substitution -5- methyl pyrrolidones N- methyl similar with structure
After the purposes of pyrrolidones, it is believed that it is " material of great attention ".Particularly, the pyrrolidones of N- alkyl -5- methyl -2, it is
The important intermediate of important industrial solvent, surfactant, complexing agent and complex functionality compound, is widely applied to such as printing
The field such as ink and fibre fuel.Therefore, N- substitution -5- methyl pyrrolidones are prepared by important industrial chemicals and its is spread out
The biological research so as to substitute oil product has far reaching significance.
Tradition prepares the temperature of the method for reaction of N- substitution -5- methyl pyrrolidones, pressure force-summing device to be had very
Requirement high.Industrially, 1-METHYLPYRROLIDONE（NMP）Two can be divided to by gamma-butyrolacton and methylamine catalyst-free synthesis NMP
Step is carried out.At a temperature of -15 DEG C, gamma-butyrolacton generates 4- hydroxy-N-methvl butyramides to the first step with the open loop of methylamine ammonolysis；The
Two 250 DEG C of step reaction temperatures, pressure 5.88MPa are prepared, but the preparation method is to the selection of equipment, the operation of process
Requirement higher is proposed with control, investment is increased.
In recent years, transition metal Ni, Cu, Rh, Ru, Ir, Pt are supported on silica, alundum (Al2O3) or activated carbon
On, the reduction amination and levulic acid of levulic acid and the reaction of alkyl nitrile or aryl nitrile can be all catalyzed, wherein more representative
Work be Manzer groups development metallic catalyst.Although forefathers have obtained the achievement attracted attention, development more efficient cryogenic
Catalyst system and catalyzing levulic acid is converted into pyrrolidones there is important industrial application value.
The content of the invention
To solve problems of the prior art, the invention provides one kind at a lower temperature, with amine as raw material,
The method that pyrrolidones is prepared using levulic acid, concrete technical scheme is as follows：
A kind of method that utilization levulic acid prepares pyrrolidones, is that the buffering of formic acid is molten in 50 DEG C~220 DEG C in temperature conditionss
In liquid system, with amine as raw material, and levulic acid is converted into N- substitution -5- methyl under the catalysis of half sandwich iridium catalyst
Pyrrolidones.
Used as the improvement of above-mentioned technical proposal, the amine is selected from one or more in aromatic amine and fatty amine.
Used as the improvement of above-mentioned technical proposal, the aromatic amine includes aniline, benzene methanamine, 2-aminotoluene, 2- methoxyl groups
Aniline, 2- bromanilines, 2- chloroanilines, 2- nitroanilines, m-chloroaniline, meta nitro aniline, meta-methoxy benzene methanamine, a chlorobenzene
Amine, meta-aminotoluene, para-totuidine, P-nethoxyaniline, para-bromoaniline, to methoxybenzylamine, parachloroanilinum.
Used as the improvement of above-mentioned technical proposal, the fatty amine includes propylamine, isopropylamine, butylamine, hexylamine, cyclohexylamine.
Used as the improvement of above-mentioned technical proposal, the half sandwich iridium catalyst is [Cp*Ir- (di-OMe-bpy)
(OH2)][SO4] or [Cp*Ir- (di-OH-bpy) (OH2)][SO4] in one or more.
Used as the improvement of above-mentioned technical proposal, the temperature conditionss are 40 DEG C~130 DEG C.
Used as the improvement of above-mentioned technical proposal, the catalyst is 0.01~1 with the molal weight ratio of amine：1.
Used as the improvement of above-mentioned technical proposal, the pH scopes of the formic acid buffer solution are 1~14.
Used as the improvement of above-mentioned technical proposal, the pH scopes of the formic acid buffer solution are 2~8.
Used as the improvement of above-mentioned technical proposal, the amine is 1~10 with the molal weight ratio of levulic acid：1.
Above-mentioned technical proposal is catalyst with half sandwich iridium catalyst, in temperature 50 in formic acid buffer solution system
DEG C~220 DEG C of temperature conditionss under, N- substitution -5- methyl pyrrolidones are obtained by levulic acid conversion, product convenient separation is produced
Rate is high, with application value higher, process is simple, wide market.
Brief description of the drawings
Fig. 1 is iridium catalyst [Cp*Ir- (di-OMe-bpy) (OH in the present invention2)][SO4] structure chart；
Fig. 2 is iridium catalyst [Cp*Ir- (di-OH-bpy) (OH in the present invention2)][SO4] structure chart；
Fig. 3 is the reaction equation of preparation method of the present invention.
Specific embodiment
Implementation process of the present invention is described further with reference to specific embodiment, the abbreviation title in embodiment is illustrated
It is as follows：
Cp：Pentamethylcyclopentadiene base；
bpy：2,2'- bipyridyls；
di-OMe-bpy：4,4'- dimethoxy -2,2'- bipyridyls；
di-OH-bpy：4,4'- dihydroxy -2,2'- bipyridyls；
LA：Levulic acid；
GC：Gas chromatography.
Embodiment 1
1mmol levulic acids, 2mmol aniline, 1 μm of ol [Cp*Ir- (di-OMe-bpy) are added in 15mL pressure pipes
(OH2)][SO4] catalyst（The catalyst structure is as shown in Figure 1）, the formic acid buffer solution that 2mLpH is 3, under magnetic agitation heat
To 120 DEG C, stir speed (S.S.) 800r/min continues constant temperature stirring reaction 4h, and it is as shown in Figure 3 that product prepares equation.
Room temperature is cooled to after the completion of reaction, room temperature is naturally cooled to, the pyrrolidones of internal standard 1- methyl -2 is added directly into
In reaction solution, 10ml methyl alcohol is added, quantitative determination is carried out to reaction system compound using gas-chromatography after being well mixed, detected
Method is as follows：
Gas phase condition：It is qualitative with standard items correspondence appearance time, it is interior scalar quantity with 1-Methyl-2-Pyrrolidone；
Heating schedule：After 120 DEG C of initial temperature retains 1 minute, it is warming up to 230 DEG C with 8 DEG C/min of speed and retains 4 minutes, amounts to
Analysis time is 22.75min；
Pressure：62.6 Kpa, total flow：77.4mL/min, column flow：1.46mL/min, linear velocity：30.0cm/sec, shunting
Than：50.0；
Gas-chromatography：Gas chromatograph is produced for Shimadzu Corporation, and INSTRUMENT MODEL is Shimadzu GC-2014, and chromatographic column is purchased from Agilent
Science and Technology Ltd., model DB-FFAP（30 m×0.320 mm×0.25µm）, batch 123-3232；In the gas phase condition
Under relative correction factor determine：（Internal standard：1-Methyl-2-Pyrrolidone）, the relative correction factor of each reagent is shown in Table 1.
The relative correction factor of each reagent of table 1
Note：
By GC（Gas chromatography）The present embodiment product is determined for N- phenyl -5- methyl-pyrrolidons, and N- phenyl -5-
The yield of methyl-pyrrolidon is 74.23%.
Embodiment 2
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, differs only in aniline
Consumption is changed to 1mL.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 54.05%.
Embodiment 3
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 4, differs only in [Cp*Ir-
(di-OMe-bpy)(OH2)][SO4] consumption of catalyst is changed to 0.5 μm of ol.After testing, products therefrom is N- phenyl -5- first
Base-pyrrolidones, and yield is 22.15%.
Embodiment 4
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 4, differs only in [Cp*Ir-
(di-OMe-bpy)(OH2)][SO4] consumption of catalyst is changed to 0.1 μm of ol.After testing, products therefrom is N- phenyl -5- first
Base-pyrrolidones, and yield is 7.23%.
Embodiment 5
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 4, differs only in [Cp*Ir-
(di-OMe-bpy)(OH2)][SO4] consumption of catalyst is changed to 0 μm of ol.After testing, N- phenyl -5- methyl-pyrrolidons
Yield is 0%.
Embodiment 6
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, differs only in and uses formic acid
The pH value of cushioning liquid is 2.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 51.30%.
Embodiment 7
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, differs only in and uses formic acid
The pH value of cushioning liquid is 4.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 59.71%.
Embodiment 8
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, differs only in and uses formic acid
The pH value of cushioning liquid is 5.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 46.95%.
Embodiment 9
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, differs only in and uses formic acid
The pH value of cushioning liquid is 6.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 27.70%.
Embodiment 10
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, differs only in and uses formic acid
The pH value of cushioning liquid is 7.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 13.41%.
Embodiment 11
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, differs only in and uses formic acid
The pH value of cushioning liquid is 8.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 4.65%.
Above-described embodiment 1 to embodiment 11 reaction condition and the results are shown in Table 2.
The reaction condition and result of the embodiment 1~11 of table 2
From embodiment 1~11 as can be seen that substrate is aniline, aniline：Levulic acid is 2:1, formic acid buffer pH value of solution is 3,120
DEG C reaction 4h when, yield highest.When catalyst is not added with, under the reaction conditions, reaction cannot obtain N- phenyl -5- first
Base-pyrrolidones.
Embodiment 12
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, differs only in only by temperature
It is changed to 100 DEG C.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 66.07%.
Embodiment 13
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, differs only in only by temperature
It is changed to 80 DEG C.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 44.31%.
Embodiment 14
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, differs only in only by temperature
It is changed to 60 DEG C.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 29.07%.
Embodiment 15
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, differs only in only by temperature
It is changed to 40 DEG C.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 11.08%.
Embodiment 16
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, differs only in only by temperature
It is changed to 130 DEG C.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 76.03%.
Embodiment 17
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, and differing only in only will reaction
Time is changed to 1h.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 10.67%.
Embodiment 18
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, and differing only in only will reaction
Time is changed to 2h.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 39.56%.
Embodiment 19
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, and differing only in only will reaction
Time is changed to 3h.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 54.87%.
Embodiment 20
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, and differing only in only will reaction
Time is changed to 5h.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 78.93 %.
Embodiment 21
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, and differing only in only will reaction
Time is changed to 6h.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 94.15%.
Embodiment 22
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, and differing only in only will reaction
Time is changed to 7h.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 90.12%.
Embodiment 23
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, and differing only in only will reaction
Time is changed to 8h.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 86.54%.
Embodiment 24
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, and differing only in only will reaction
Time is changed to 9h.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 65.29%.
Embodiment 25
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, and differing only in only will reaction
Time is changed to 10h.After testing, products therefrom is N- phenyl -5- methyl-pyrrolidons, and yield is 30.21%.
Above-described embodiment 12 to embodiment 25 reaction condition and the results are shown in Table 3.
The reaction condition and result of the embodiment 12~25 of table 3
From embodiment 12~25 as can be seen that catalyst [Cp*Ir- (di-OMe-bpy) (OH2)][SO4] it is 1 μm of ol, 120 DEG C
It is 94.15% that reaction 4h be converted into aniline N- phenyl -5- methyl-pyrrolidons to have highest yield；Reduce the temperature to 40
DEG C, the yield of N- phenyl -5- methyl-pyrrolidons only has 11.08%, when reacted between when extending to 10h, N- phenyl -5- first
The yield of base-pyrrolidones only has 30.21%, and too low reaction temperature and reaction time more long is unfavorable for N- phenyl -5- first
The generation of base-pyrrolidones.
Embodiment 26
The present embodiment is prepared to methyl -5- methyl pyrrolidones by the identical mode of embodiment 1, is differed only in and is only changed aniline
It is para-totuidine.After testing, products therefrom be to methyl -5- methyl pyrrolidones, and yield be 70.69%.
Embodiment 27
The present embodiment is prepared to methoxyl group -5- methyl pyrrolidones by the identical mode of embodiment 1, is differed only in only by aniline
It is changed to P-nethoxyaniline.After testing, products therefrom be to methoxyl group -5- methyl pyrrolidones, and yield be 64.67%.
Embodiment 28
The present embodiment is prepared to bromo- 5- methyl pyrrolidones by the identical mode of embodiment 1, is differed only in and is only changed to aniline
Para-bromoaniline.After testing, products therefrom be to bromo- 5- methyl pyrrolidones, and yield be 47.89%.
Embodiment 29
The present embodiment by the identical mode of embodiment 1 prepare between chloro- 5- methyl pyrrolidones, differ only in and be only changed to aniline
M-chloroaniline.After testing, chloro- 5- methyl pyrrolidones between products therefrom is, and yield is 55.92%.
Embodiment 30
The present embodiment prepares a nitro -5- methyl pyrrolidone by the identical mode of embodiment 1, differs only in and only changes aniline
It is meta nitro aniline.After testing, nitro -5- methyl pyrrolidones between products therefrom is, and yield is 42.18%.
Embodiment 31
The present embodiment prepares benzyl -5- methyl pyrrolidones by the identical mode of embodiment 1, differs only in and only changes aniline
It is benzene methanamine.After testing, products therefrom is benzyl -5- methyl pyrrolidones, and yield is 74.27%.
Embodiment 32
The present embodiment is prepared to methoxyl group -5- methyl pyrrolidones by the identical mode of embodiment 1, is differed only in only by aniline
It is changed to methoxybenzylamine.After testing, products therefrom be to methoxyl group -5- methyl pyrrolidones, and yield be 76.29%.
Embodiment 33
The present embodiment is prepared to chloro- 5- methyl pyrrolidones by the identical mode of embodiment 1, is differed only in and is only changed to aniline
Parachloroanilinum.After testing, products therefrom be to chloro- 5- methyl pyrrolidones, and yield be 61.25%.
Embodiment 34
The present embodiment prepares propyl group -5- methyl pyrrolidones by the identical mode of embodiment 1, differs only in and is only changed to aniline
Propylamine.After testing, products therefrom is propyl group -5- methyl pyrrolidones, and yield is 89.70%.
Embodiment 35
The present embodiment prepares isopropyl -5- methyl pyrrolidones by the identical mode of embodiment 1, differs only in and only changes aniline
It is isopropylamine.After testing, products therefrom is isopropyl -5- methyl pyrrolidones, and yield is 44.35%.
Embodiment 36
The present embodiment prepares butyl -5- methyl pyrrolidones by the identical mode of embodiment 1, differs only in and is only changed to aniline
Butylamine.After testing, products therefrom is butyl -5- methyl pyrrolidones, and yield is 88.39%.
Embodiment 37
The present embodiment prepares hexyl -5- methyl pyrrolidones by the identical mode of embodiment 1, differs only in and is only changed to aniline
Hexylamine.After testing, products therefrom is hexyl -5- methyl pyrrolidones, and yield is 65.29%.
Embodiment 38
The present embodiment prepares cyclohexyl -5- methyl pyrrolidones by the identical mode of embodiment 1, differs only in and only changes aniline
It is cyclohexylamine.After testing, products therefrom is cyclohexyl -5- methyl pyrrolidones, and yield is 21.37%.
Embodiment 39
The present embodiment prepares N- phenyl -5- methyl-pyrrolidons by the identical mode of embodiment 1, and differing only in only will catalysis
Agent is changed to [Cp*Ir- (di-OH-bpy) (OH2)][SO4], the catalyst structure is as shown in Fig. 2 after testing, products therefrom is N-
Phenyl -5- methyl-pyrrolidons, and yield is 67.45%.
Above-described embodiment 26 to embodiment 39 reaction condition and the results are shown in Table 4.
The reaction condition and result of the embodiment 26~39 of table 4
By embodiment 26~39 as can be seen that catalyst [Cp*Ir- (di-OMe-bpy) (OH2)][SO4] in same reaction bar
Under part, catalytic effect is better than [Cp*Ir- (di-OH-bpy) (OH2)][SO4].The catalyst system and catalyzing is also same for other amine substrates
Sample is applicable.
It should be noted that above-mentioned simply presently preferred embodiments of the present invention, not makees any formal limit to the present invention
System.Any those of ordinary skill in the art, in the case where technical solution of the present invention scope is not departed from, take off using above-mentioned
The technology contents for showing make many possible variations and modification, or the equivalent reality for being revised as equivalent variations to technical solution of the present invention
Apply example.Therefore, every content without departing from technical solution of the present invention, according to the technology of the present invention essence to made for any of the above embodiments
Any simple modification, equivalent variation and modification, all should fall in the range of technical solution of the present invention protection.
Claims (10)
1. a kind of method that utilization levulic acid prepares pyrrolidones, it is characterised in that temperature conditionss be 50 DEG C~220 DEG C
Interior, in the buffer solution system of formic acid, with amine as raw material, and levulic acid is converted under the catalysis of half sandwich iridium catalyst
For N- replaces -5- methyl pyrrolidones.
2. the method that a kind of utilization levulic acid as claimed in claim 1 prepares pyrrolidones, it is characterised in that the amine choosing
One or more from aromatic amine and fatty amine.
3. the method that a kind of utilization levulic acid as claimed in claim 2 prepares pyrrolidones, it is characterised in that the fragrance
Amine includes aniline, benzene methanamine, 2-aminotoluene, 2- aminoanisoles, 2- bromanilines, 2- chloroanilines, 2- nitroanilines, a chlorobenzene
Amine, meta nitro aniline, meta-methoxy benzene methanamine, m-chloroaniline, meta-aminotoluene, para-totuidine, P-nethoxyaniline, to bromobenzene
Amine, to methoxybenzylamine, parachloroanilinum.
4. the method that a kind of utilization levulic acid as claimed in claim 2 prepares pyrrolidones, it is characterised in that the fat
Amine includes propylamine, isopropylamine, butylamine, hexylamine, cyclohexylamine.
5. the method that a kind of utilization levulic acid as claimed in claim 3 prepares pyrrolidones, it is characterised in that described half three
Mingzhi's iridium catalyst is [Cp*Ir- (di-OMe-bpy) (OH2)][SO4] or [Cp*Ir- (di-OH-bpy) (OH2)][SO4] in
One or more.
6. the method that a kind of utilization levulic acid as claimed in claim 1 prepares pyrrolidones, it is characterised in that the temperature
Condition is 40 DEG C~130 DEG C.
7. the method that a kind of utilization levulic acid as claimed in claim 1 prepares pyrrolidones, it is characterised in that the catalysis
Agent is 0.01~1 with the molal weight ratio of amine：1.
8. the method that a kind of utilization levulic acid as claimed in claim 1 prepares pyrrolidones, it is characterised in that the formic acid
The pH scopes of cushioning liquid are 1~14.
9. the method that a kind of utilization levulic acid as claimed in claim 8 prepares pyrrolidones, it is characterised in that the formic acid
The pH scopes of cushioning liquid are 2~8.
10. the method that a kind of utilization levulic acid as claimed in claim 1 prepares pyrrolidones, it is characterised in that the amine
Class is 1~10 with the molal weight ratio of levulic acid：1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115709077A (en) * | 2022-10-21 | 2023-02-24 | 中国科学院广州能源研究所 | Method for preparing 5-methyl-N-substituted pyrrolidone compound |
Citations (1)
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|---|---|---|---|---|
| CN105712854A (en) * | 2016-01-25 | 2016-06-29 | 中国科学技术大学先进技术研究院 | Method for selectively preparing 1-hydroxyl-2, 5-hexanedione and 2, 5-furandimethanol |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105712854A (en) * | 2016-01-25 | 2016-06-29 | 中国科学技术大学先进技术研究院 | Method for selectively preparing 1-hydroxyl-2, 5-hexanedione and 2, 5-furandimethanol |
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| YAWEN WEI ET AL.: "Highly efficient transformation of levulinic acid into pyrrolidinones by iridium catalysed transfer hydrogenation", 《CHEM. COMMUN.》 * |
| 魏雅雯: "新型转移氢化反应及其应用研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115709077A (en) * | 2022-10-21 | 2023-02-24 | 中国科学院广州能源研究所 | Method for preparing 5-methyl-N-substituted pyrrolidone compound |
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