CN110407678A - 2- cyclopentene-1-one is continuously synthesizing to method - Google Patents
2- cyclopentene-1-one is continuously synthesizing to method Download PDFInfo
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- CN110407678A CN110407678A CN201910785554.XA CN201910785554A CN110407678A CN 110407678 A CN110407678 A CN 110407678A CN 201910785554 A CN201910785554 A CN 201910785554A CN 110407678 A CN110407678 A CN 110407678A
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- cyclopentene
- continuously synthesizing
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- copper
- oxidation reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Method is continuously synthesizing to the present invention provides a kind of 2- cyclopentene-1-one.It includes: that catalyst is loaded into continuous reacting device that this, which is continuously synthesizing to method, is then continuously delivered to cyclopentene, oxidant and solvent to carry out oxidation reaction in continuous reacting device, and 2- cyclopentene-1-one is continuously discharged.In the presence of catalysts and solvents, using cyclopentene as starting material, and it is made directly to carry out oxidation reaction with oxidant, can be avoided the generation of the largely three wastes containing halogen；It is entirely continuously synthesizing to the generation of security risk when process carries out that amplification can effectively be inhibited to produce in continuous reacting device simultaneously；Furthermore, after the reaction was completed, target product (2- cyclopentene-1-one) can be obtained through simple concentration in the product system of oxidation reaction, to greatly improve the purity (up to 98% or more) and separation rate (up to 79%) of product, and is easy to amplify production.
Description
Technical field
The present invention relates to medicine intermediates to synthesize field, in particular to a kind of continuous chemical combination of 2- cyclopentene-1-one
At method.
Background technique
2- cyclopentene-1-one can be used as the raw material of various pharmaceuticals and functional material.Industrial production at present mainly with
Cyclopentanone is starting material, and alpha-halogenate cyclopentanone is obtained after halogenated, elimination reaction then occurs under alkaline condition.The synthesis
The halogen three wastes of method are larger, and used solvent n,N-Dimethylformamide relatively difficult, finished product when separating in the later period
Exist with the N,N-dimethylformamide solution of product.Existing document optimizes the technique, using boiling point at 145 DEG C or less
Fragrant series solvent and boiling point be used cooperatively in 180 DEG C~240 DEG C of acid amides series solvent, with achieve the purpose that the later period separate, point
From yield 51%~58%, and utilize the solvent reclamation being concentrated under reduced pressure out.Separately there is document using cyclopentene as raw material, Pd (acetic acid
Palladium, palladium dydroxide, palladium carbon etc.) catalyst is made, it aoxidizes to obtain 2- cyclopentene-1-one through tert-butyl hydroperoxide, total recovery is
71%, this method is relatively easy, but wherein palladium catalyst is expensive, and reaction is oxidant using tert-Butanol peroxide, and there are one
Determine security risk, production should not be amplified.
In conclusion the synthetic method of 2- cyclopentene-1-one there are separation yields lower, high production cost and having one at present
The problem of determining security risk.Therefore, the practicable process route for being suitable for industrialized production is developed to be of great significance.
Summary of the invention
It is continuously synthesizing to method the main purpose of the present invention is to provide a kind of 2- cyclopentene-1-one, it is existing to solve
There is lower separation yield, high production cost and have certain security risk in the synthetic method of 2- cyclopentene-1-one.
To achieve the goals above, method, serialization are continuously synthesizing to the present invention provides a kind of 2- cyclopentene-1-one
Synthetic method includes: that catalyst is loaded into continuous reacting device, then that cyclopentene, oxidant and solvent is continuously defeated
It send into continuous reacting device and carries out oxidation reaction, and 2- cyclopentene-1-one is continuously discharged.
Further, the ratio between molal quantity of cyclopentene and oxidant is 1:(2~20).
Further, oxidant is selected from tert-butyl hydroperoxide, hydrogen peroxide, hydrogen peroxide urea, sodium hypochlorite, m-chloro mistake
One of oxybenzoic acid, Peracetic acid, group of ozone and oxygen composition are a variety of.
Further, the temperature of oxidation reaction is 0~100 DEG C.
Further, the temperature of oxidation reaction is 30~80 DEG C.
Further, the residence time of reaction mass is 15~40min in continuous reacting device.
Further, the dosage of catalyst is 0.1~10mol%.
Further, catalyst is selected from elemental copper, cuprous halide, cuprous oxide, cuprous cyanide, copper halide, copper acetate, sulphur
One of group of sour copper, copper nitrate, copper oxide and trifluoroacetic acid copper composition is a variety of.
Further, solvent is selected from water, methylene chloride, 1,2- dichloroethanes, ethyl acetate, chloroform, hexamethylene, four
Hydrogen furans, 2- methyltetrahydrofuran, 1,4- dioxane, glycol dimethyl ether, diethylene glycol dimethyl ether, benzene, toluene, diformazan
Benzene, acetone, acetonitrile, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N, N- diethylformamide, N- crassitude
One of group of ketone, dimethyl sulfoxide, methanol, ethyl alcohol and isopropanol composition is a variety of.
Further, it is continuously synthesizing to method further include: quencher is added in the product system of oxidation reaction and quenches
It goes out reaction, obtains 2- cyclopentene-1-one.
It applies the technical scheme of the present invention, it is above-mentioned to be continuously synthesizing in method, in the presence of catalysts and solvents, with ring
Amylene is starting material, and it is made directly to carry out oxidation reaction with oxidant, can be avoided the generation of the largely three wastes containing halogen；Together
When be entirely continuously synthesizing to the hair of security risk when process carries out effectively inhibiting in continuous reacting device amplification to produce
It is raw；In addition, after the reaction was completed, target product (2- cyclopentene -1- can be obtained through simple concentration in the product system of oxidation reaction
Ketone), to greatly improve the purity (up to 98% or more) and separation rate (up to 79%) of product, and it is easy to amplify life
It produces.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As described in background technique, that there are separation yields is lower, raw for the synthetic method of existing 2- cyclopentene-1-one
It produces at high cost and has the problem of certain security risk.In order to solve the above-mentioned technical problem, this application provides a kind of 2- cyclopentene-
1- ketone is continuously synthesizing to method, and it includes: that catalyst is loaded into continuous reacting device that this, which is continuously synthesizing to method, then
Cyclopentene, oxidant and solvent are continuously delivered to carry out oxidation reaction in continuous reacting device, and 2- ring is continuously discharged
Amylene -1- ketone.
The above-mentioned synthetic route for being continuously synthesizing to method is as follows:
It is above-mentioned to be continuously synthesizing in method, in the presence of catalysts and solvents, using cyclopentene as starting material, and make it
Oxidation reaction is directly carried out with oxidant, can be avoided the generation of the largely three wastes containing halogen；It is entirely continuously synthesizing to process simultaneously
The generation of security risk when in continuous reacting device carrying out that amplification can effectively be inhibited to produce；In addition, after the reaction was completed, oxygen
Target product (2- cyclopentene-1-one) can be obtained through simple concentration in the product system for changing reaction, to greatly improve production
The purity (up to 98% or more) and separation rate (up to 79%) of product, and it is easy to amplify production.
Above-mentioned continuous reacting device can use type commonly used in the art.Preferably, above-mentioned continuous reaction device is
Load column.Device is used compared to other serializations, is conducive to purity, the separative efficiency of further deduction product using load column
And safety.
In a kind of preferred embodiment, the ratio between molal quantity of cyclopentene and oxidant is 1:(2~20).Cyclopentene and oxygen
The ratio between molal quantity of agent includes but is not limited to above range, and is limited and be conducive to further increase ring within the above range
The conversion ratio of amylene and the yield of 2- cyclopentene-1-one.
In a kind of preferred embodiment, oxidant includes but is not limited to tert-butyl hydroperoxide, hydrogen peroxide, hydrogen peroxide
One of urea, sodium hypochlorite, metachloroperbenzoic acid, Peracetic acid, group of ozone and oxygen composition are a variety of.Compared to
Other oxidants select above-mentioned several oxidants to be conducive to improve the extent of reaction of oxidation reaction, and improve 2- cyclopentene-1-one
Yield.It is highly preferred that it is 50~100% tert-butyl hydroperoxide that above-mentioned oxidant, which is concentration,.
In a kind of preferred embodiment, the temperature of oxidation reaction is 0~100 DEG C.Compared to other temperature ranges, by it
Limit the extent of reaction for being conducive to further increase oxidation reaction within the above range.It is highly preferred that the temperature of oxidation reaction is
30~80 DEG C.
In a kind of preferred embodiment, the residence time of reaction mass is 15~40min in continuous reacting device.Even
The residence time of reaction mass includes but is not limited to above range in continuousization reaction unit, and limited has within the above range
Conducive to the extent of reaction of raising reaction raw materials, while improving the yield of 2- cyclopentene-1-one.
In a kind of preferred embodiment, the dosage of catalyst is 0.1~10mol%.Compared to other ranges, will be catalyzed
The dosage of agent limits the reaction rate for being conducive to improve oxidation reaction within the above range, and then can shorten process cycle.
Above-mentioned to be continuously synthesizing in method, catalyst can select type commonly used in the art.In a kind of preferred implementation
In example, catalyst includes but is not limited to elemental copper, cuprous halide, cuprous oxide, cuprous cyanide, copper halide, copper acetate, sulfuric acid
One of group of copper, copper nitrate, copper oxide and trifluoroacetic acid copper composition is a variety of.It is urged using cheap copper catalyst substitution palladium
Agent can greatly save production cost.
Above-mentioned to be continuously synthesizing in method, solvent can select type commonly used in the art.In a kind of preferred embodiment
In, solvent includes but is not limited to water, methylene chloride, 1,2- dichloroethanes, ethyl acetate, chloroform, hexamethylene, tetrahydro furan
It mutters, 2- methyltetrahydrofuran, 1,4- dioxane, glycol dimethyl ether, diethylene glycol dimethyl ether, benzene,toluene,xylene, third
Ketone, acetonitrile, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N, N- diethylformamide, N-Methyl pyrrolidone, two
One of group of methyl sulfoxide, methanol, ethyl alcohol and isopropanol composition is a variety of.
In order to improve the purity of 2- cyclopentene-1-one, it is preferable that above-mentioned to be continuously synthesizing to method further include: anti-in oxidation
Quencher is added in the product system answered and carries out quenching reaction, obtains 2- cyclopentene-1-one.
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally
Apply for range claimed.
Embodiment 1
At room temperature, copper catalyst (cuprous iodide particle, 80 mesh, 8.39g, 44.0mmol) is loaded in load column, control
The column temperature of system load column is 45 DEG C or so.
By compound A (30.00g, 440.4mmol), tert-butyl hydroperoxide (70% aqueous solution, 283.49g,
It 2202.0mmol) is uniformly mixed with acetonitrile (180ml, 6V), obtains reaction raw materials, it is spare；It is using plunger pump that above-mentioned reaction is former
Material is persistently pumped into load column, and makes its residence time 30.0min in load column.In the discharge port sampling of load column, and
It is tracked and is reacted using GC.After charging, it is cooled to room temperature the temperature of product system, 10% sodium sulfite is added dropwise thereto
Aqueous solution, system liquid separation, obtains organic phase.Organic phase is concentrated under conditions of T≤45 DEG C, P≤- 0.08MPa, must produce
Object 28.71g, internal standard content are 99.5%, yield 79.00%.
Embodiment 2
At room temperature, copper catalyst (cuprous iodide particle, 80 mesh, 8.39g, 44.0mmol) is loaded in load column, control
The column temperature of system load column is 45 DEG C or so.
By compound A (30.00g, 440.4mmol), tert-butyl hydroperoxide (70% aqueous solution, 56.70g,
It 440.4mmol) is uniformly mixed with acetonitrile (180ml, 6V), obtains reaction raw materials, it is spare；Using plunger pump by above-mentioned reaction raw materials
It is persistently pumped into load column, and makes its residence time 30.0min in load column.In the discharge port sampling of load column, and make
It is tracked and is reacted with GC.After charging, it is cooled to room temperature the temperature of product system, 10% sodium sulfite water is added dropwise thereto
Solution, system liquid separation, obtains organic phase.Organic phase is concentrated under conditions of T≤45 DEG C, P≤- 0.08MPa, product is obtained
13.90g, internal standard content are 99.4%, yield 38.22%.
With the difference of embodiment 1 are as follows: the ratio between compound A and the molal quantity of tert-butyl hydroperoxide are 1:1.
Embodiment 3
At room temperature, copper catalyst (cuprous iodide particle, 80 mesh, 8.39g, 44.0mmol) is loaded in load column, control
The column temperature of system load column is 45 DEG C or so.
By compound A (30.00g, 440.4mmol), hydrogen peroxide (35% aqueous solution, 213.97g, 2202.0mmol) and
Acetonitrile (180ml, 6V) is uniformly mixed, and obtains reaction raw materials, spare；Above-mentioned reaction raw materials are persistently pumped into load using plunger pump
In column, and make its residence time 30.0min in load column.In the discharge port sampling of load column, and use GC tracking reaction.
After charging, it is cooled to room temperature the temperature of product system, 10% sodium sulfite aqueous solution is added dropwise thereto, complete body is quenched
T≤45 DEG C are tied up to, are concentrated under conditions of P≤- 0.08MPa, 7~8V of system residue (210ml~240ml) is concentrated into, to
Methylene chloride (120ml, 4V) extraction is added in system, and system liquid separation obtains organic phase.Make organic phase in T≤45 DEG C, P≤-
It is concentrated under conditions of 0.08MPa, obtains product 22.72g, internal standard content is 99.6%, yield 62.60%.
With the difference of embodiment 1 are as follows: oxidant is 35% hydrogen peroxide.
Embodiment 4
At room temperature, copper catalyst (cuprous iodide particle, 80 mesh, 8.39g, 44.0mmol) is loaded in load column, control
The column temperature of system load column is 15 DEG C or so.
By compound A (30.00g, 440.4mmol), tert-butyl hydroperoxide (70% aqueous solution, 283.49g,
It 2202.0mmol) is uniformly mixed with acetonitrile (180ml, 6V), obtains reaction raw materials, it is spare；It is using plunger pump that above-mentioned reaction is former
Material is persistently pumped into load column, and makes its residence time 30.0min in load column.In the discharge port sampling of load column, and
It is tracked and is reacted using GC.After charging, 10% sodium sulfite aqueous solution is added dropwise thereto, system liquid separation obtains organic phase.
Organic phase is concentrated under conditions of T≤45 DEG C, P≤- 0.08MPa, product 19.84g is obtained, internal standard content is 99.4%,
Yield is 54.55%.
With the difference of embodiment 1 are as follows: the temperature of oxidation reaction is 15 DEG C.
Comparative example 1
Into 250mL autoclave be added cuprous iodide (2.80g, 14.68mmol), sequentially add compound A (10.00g,
146.78mmol), acetonitrile (60ml, 6V), tert-butyl hydroperoxide (70% aqueous solution, 94.48g, 733.9mmol), unlatching is stirred
It mixes, after system is warming up to 45 DEG C, system pressure 3.0MPa, insulation reaction 1h, system pressure 8.2MPa, system pressure release uses GC
Tracking reaction.Reaction is finished, and 10% sodium sulfite aqueous solution is added dropwise thereto, and system liquid separation obtains organic phase.Organic phase is set to exist
T≤45 DEG C are concentrated under conditions of P≤- 0.08MPa, and product 22.98g is obtained, and internal standard content is 99.5%, and yield is
63.25%.
With the difference of embodiment 1 are as follows: above-mentioned oxidation reaction carries out in a kettle.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements: above-mentioned continuous
It is combined in method, in the presence of catalysts and solvents, using cyclopentene as starting material, and carries out it directly with oxidant
Oxidation reaction can be avoided the generation of the largely three wastes containing halogen；Process is entirely continuously synthesizing in continuous reacting device simultaneously
The generation of security risk when middle progress can effectively inhibit amplification to produce；In addition, after the reaction was completed, the product system of oxidation reaction
Simply be concentrated and target product (2- cyclopentene-1-one) can be obtained, thus greatly improve product purity (98% with
On) and separation rate (up to 79%), and it is easy to amplify production.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of 2- cyclopentene-1-one is continuously synthesizing to method, which is characterized in that the method that is continuously synthesizing to includes:
Catalyst is loaded into continuous reacting device, is then continuously delivered to cyclopentene, oxidant and solvent described
Oxidation reaction is carried out in continuous reacting device, and the 2- cyclopentene-1-one is continuously discharged.
2. according to claim 1 be continuously synthesizing to method, which is characterized in that the cyclopentene rubs with the oxidant
The ratio between your number is 1:(2~20).
3. according to claim 1 or 2 be continuously synthesizing to method, which is characterized in that the oxidant is selected from tert-butyl mistake
What hydrogen oxide, hydrogen peroxide, hydrogen peroxide urea, sodium hypochlorite, metachloroperbenzoic acid, Peracetic acid, ozone and oxygen formed
One of group is a variety of.
4. according to claim 1 be continuously synthesizing to method, which is characterized in that the temperature of the oxidation reaction is 0~100
℃。
5. according to claim 4 be continuously synthesizing to method, which is characterized in that the temperature of the oxidation reaction is 30~80
℃。
6. according to claim 4 or 5 be continuously synthesizing to method, which is characterized in that anti-in the continuous reacting device
The residence time for answering material is 15~40min.
7. according to any one of claim 1 to 6 be continuously synthesizing to method, which is characterized in that the use of the catalyst
Amount is 0.1~10mol%.
8. according to claim 7 be continuously synthesizing to method, which is characterized in that the catalyst is selected from elemental copper, halogenation
The group of cuprous, cuprous oxide, cuprous cyanide, copper halide, copper acetate, copper sulphate, copper nitrate, copper oxide and trifluoroacetic acid copper composition
One of or it is a variety of.
9. according to claim 1 be continuously synthesizing to method, which is characterized in that the solvent is selected from water, methylene chloride, 1,
2- dichloroethanes, ethyl acetate, chloroform, hexamethylene, tetrahydrofuran, 2- methyltetrahydrofuran, 1,4- dioxane, second two
Diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, benzene,toluene,xylene, acetone, acetonitrile, N,N-dimethylformamide, N, N- dimethyl
Acetamide, N, N- diethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide, methanol, ethyl alcohol and isopropanol composition group in
It is one or more.
10. according to claim 7 or 8 be continuously synthesizing to method, which is characterized in that the method that is continuously synthesizing to also is wrapped
It includes: quencher being added in the product system of the oxidation reaction and carries out quenching reaction, obtains the 2- cyclopentene-1-one.
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