CN102633680B - Catalyst for preparing 3,3-diethoxyl propionitrile and preparation method of catalyst - Google Patents
Catalyst for preparing 3,3-diethoxyl propionitrile and preparation method of catalyst Download PDFInfo
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Abstract
The invention discloses a method for preparing 3,3-diethoxyl propionitrile and 3-ethoxyl acrylonitrile by catalysis reaction as well as a used catalyst and a preparation method of the catalyst. The method for preparing 3,3-diethoxyl propionitrile comprises the step of carrying out acetalation reaction on acrylonitrile and ethanol in a high-pressure kettle reactor based on palladium chloride/P-V-Mo heteropoly acid as the catalyst and activated carbon as a carrier, wherein the molar ratio of acrylonitrile to ethanol is (1:25)-(1:85), the reaction temperature is 50-90 DEG C, and the oxygen pressure is 0.5-2.5Mpa when the reaction is carried out.
Description
Technical field
The present invention relates to prepare 3, the method of 3-diethoxy propionitrile and 3-ethoxy propylene nitrile, particularly catalyzed reaction is prepared 3,3-diethoxy propionitrile and 3-ethoxy propylene nitrile, and prepares the preparation method of the related catalyzer of product and this catalyzer by this method.
Background technology
3,3-diethoxy propionitrile, colourless or weak yellow liquid, boiling point 9l-93 DEG C (11mmHg), density 0.954g/ml, is the monomer of a kind of important Organic Chemicals and synthetic medicine and spices.One of them important purposes of 3,3-diethoxy propionitrile is as synthesise vitamins B
1, the important compound such as cytosine(Cyt) and derivative thereof precursor.3,3-diethoxy propionitrile and 3-ethoxy propylene nitrile are all very important medicine and makeup intermediate.Particularly, 3,3-diethoxy propionitrile and 3-ethoxy propylene nitrile are synthesise vitamins B
l, the important compound such as cytosine(Cyt) and derivative thereof precursor.Due to 3,3-diethoxy propionitrile or the stable acetal form of 3-ethoxy propylene nitrile, the form that therefore cyanoacetaldehyde is changed into 3,3-diethoxy propionitrile is prepared the multiple heterocycles such as pyrazoles, pyridine derivate compound through cyclization.In recent years, the synthetic method of 3,3-diethoxy propionitrile and 3-ethoxy propylene nitrile, mainly comprises dehydration of amide, metal cyanides replacement, etherificate acetal, processed isoxazole method, benzene sulphur sulfone propionitrile method and vinyl cyanide oxidation style etc.
Dehydration of amide nitrile method processed, taking ethyl formate, ethyl acetate as raw material, under sodium ethylate effect, through claisen condensation, then through aldol condensation, then with azanol reaction 40h, generates 3,3-diethoxy propionic acid amide, then generates 3,3-diethoxy propionitrile through dehydration.This method technical process is long, and by product is more, and the yield of final product only has 8%, is not suitable for industrialization.Referring to " The preparation; alcoholysis and reduction of cyanoacetaldehyde diethylacetal Malonaldehyde tetraethylacetal[J] " Journal of the American Chemical Society, 1947,69,2657-2660.
Metal cyanides replaces nitrile method processed, with bromoacetaldehyde diethyl acetal and sodium cyanide reaction, can make 3,3-diethoxy propionitrile.Yield 80%, but due to raw material sources difficulty, reaction not exclusively, contains the problems such as a large amount of sodium cyanides in waste liquid, be not suitable for scale production.Referring to " Methods in alkaloid synthesis.Iminoethers as donors in the Michael reaction[J] " Journal of the American Chemical Society, 1975,97,7152-7157.
Etherificate acetal method processed, taking chlorallylene nitrile as raw material: sodium ethylate is slowly joined in chlorallylene nitrile, 30 DEG C time, react 4h, be neutralized to pH=8 with acetic acid, remove by filter the Sodium chloride deposit in solution, alcohol solvent is removed in underpressure distillation, and the residual liquid that obtains is 3,3-diethoxy propionitrile, the yield of this reaction is about 77%.Referring to " Synthesis of acetals of cyanoacetaldehyde[P] " Frank Scotti, Joseph Frazza Everett.US3138616,1964206223.Taking acyloxy vinyl cyanide as raw material: taking acyloxy vinyl cyanide and ethanol as substrate, HCl are as catalyzer, 78 DEG C of reaction 3h can make 3,3-diethoxy propionitrile, and this reactions steps is simple, and condition is easily controlled, and the reaction times is shorter, and yield can reach 88%.But due to the synthetic difficulty of reaction substrate acyloxy vinyl cyanide, price is higher all the time, has limited the industrial prospect of the method.Therefore the best process flow of, seeking synthetic acyloxy vinyl cyanide is the key of this path industrial application.Referring to " Method of preparing acetals and enolethers from acyloxymethylene compounds [P] " Hermann Peeters, Niederkassel, Wilhelm Vogt.US 4534910,1985208213.Taking acetonitrile as raw material: in airtight reactor, add acetonitrile, sodium methylate, ethyl formate etc., at 4MPa, 60 DEG C, be constantly filled with CO gas until saturated and then and monochloroethane reaction generate acetal, this overall yield of reaction is about 73.4%.Because needs carry out under high pressure and catalyzer existence, reaction conditions is relatively harsh.Referring to " Process for the synthesis of cyanoacetaldehyde acetals[P] " Itter Franz-Albert, Breuer Joachim.DE 3641604 (A1), 19861205.Domestic 3, the production of 3-diethoxy propionitrile mainly adopts this technique.The main drawback that this synthesis route exists is that production yield is low, and effect is poor, and aftertreatment is more loaded down with trivial details, and production cost is higher, has certain problem of environmental pollution.
Oxazole open loop method, with 1,1,3,3-tetraethoxypropane and hydroxylamine hydrochloride reaction, the mixture of Sheng isoxazole, then with ethyl sulfate reaction, through aftertreatment, can obtain 3, the mixture of 3-diethoxy propionitrile and 3-ethoxy propylene nitrile, total recovery 85-90%, raw materials used 1,1,3,3-tetraethoxypropane price is higher, be difficult to obtain, limited the industrial applications prospect of this method.Referring to " analysis of 3-ethoxy propylene nitrile and 3,3-diethoxy propionitrile mixture " fine-chemical intermediate .2007,37 (6): 65-68; " 3,3-diethoxy propionitrile " meticulous with specialty chemicals .2007,15 (5), 11-14.
Benzene sulphur sulfone propionitrile method, taking the chloro-3-phenyl of 2-sulphur sulfuryl propionitrile as raw material, through eliminating and addition two-step reaction, synthesizes 3,3-diethoxy propionitrile, total recovery 88%.Referring to " synthesizing of 3,3-dimethoxy propionitrile " fuel and dyeing, 2005,42 (5), 41-42.Because the chloro-3-phenyl of 2-sulphur sulfuryl propionitrile will be through the addition of vinyl cyanide chloro, displacement, the preparation of oxidation three-step reaction, in fact processing step is very long, has a large amount of by products to generate, and is not suitable for scale production.
Vinyl cyanide oxidation style, this method is taking vinyl cyanide, ethanol and oxygen as raw material, and by the effect of Palladous chloride and cuprous chloride or copper chloride catalyst, at 60 DEG C, reaction 20h, obtains 3 of certain yield, 3-diethoxy propionitrile.Referring to " ア セ
one Le Class System making method [P] " on Fuchi height just, Hu Nanxing, Pu Tian Shangnan .JP06087781; Along with further development, in this type of reaction, for fear of the corrodibility of chlorion, oxygenant chlorination copper is by polymeric oxide, the replacements such as heteropolyacid.
The ubiquitous deficiency of prior art is that speed of reaction is low, consuming time long, and yield is relatively low.
Summary of the invention
The invention provides one and can overcome existingly 3,3-diethoxy propionitrile is produced the long deficiency of required time, can synthesize 3,3-diethoxy propionitrile, and Reaction time shorten greatly, improves the method for speed of reaction; The present invention provides the preparation method of this catalyzer that this method is used and this catalyzer simultaneously.
Of the present inventionly prepare 3 with catalysis synthesis process, the method of 3-diethoxy propionitrile be with Palladous chloride/phosphorus molybdenum vanadium heteropolyacid be catalyzer, gac is support of the catalyst, in autoclave reactor, make vinyl cyanide and ethanol generation acetalation, the molar ratio of vinyl cyanide and ethanol is 1: 25～l: 85, temperature of reaction is 50～90 DEG C, when reaction, oxygen pressure is 0.5～2.5Mpa, formula 1 is shown in its reaction, in formula, 1 is vinyl cyanide, 2 is 3,3-diethoxy propionitrile, and 3a and 3b are respectively the cis-trans-isomer of 3-ethoxy propylene nitrile.
Formula 1
The preferred reaction conditions that catalysis synthesis process of the present invention is prepared 3,3-diethoxy propionitrile is: add Palladous chloride/phosphorus molybdenum vanadium heteropolyacid catalyzer of 0.2g, 2.0mmol vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene, oxygen pressure is 2.0MPa, temperature of reaction is 60 DEG C.
Palladous chloride/phosphorus molybdenum vanadium heteropolyacid catalyzer that the present invention is used, wherein Palladous chloride molecular formula is PdCl
2, heteropolyacid molecular formula is H
3+npMo
12-nv
no
40, n=1-3, utilizes pickling process, successively Palladous chloride and heteropolyacid is carried on gac with the form of solution, and the palladium content on gac is 2.0-6.6wt.%, and heteropolyacid is 10-20wt.%.
Palladous chloride/phosphorus molybdenum vanadium heteropolyacid method for preparing catalyst of the present invention is:
First take in proportion molybdic oxide and Vanadium Pentoxide in FLAKES and be dispersed in deionized water, be heated to 100 DEG C of backflows; Then, adding content is 85% phosphoric acid solution, continues after back flow reaction 24h, to obtain the brick red solution of clarification at this temperature, and prepared solution is carried out to recrystallization, and crystalline material, through drying treatment, obtains required phosphorus molybdenum vanadium heteropolyacid;
The Palladous chloride of getting 0.4mmol is dissolved in deionized water, then add the gac of 0.8g amount in palladium chloride solution, after at room temperature stirring dipping 6h, after the phosphorus molybdenum vanadium heteropolyacid that 0.08mmol is prepared as stated above dissolves with 20ml deionization, add in above-mentioned system, continue to stir and spend the night.Finally will flood system after filtration, washing, dry, the solid matter obtaining is required catalyzer finished product.
The preparation method of phosphorus molybdenum vanadium heteropolyacid of the present invention can reference, " Hydroxylation of Benzene with Hydrogen Peroxide over Highly Efficient Molybdovanadophosphoric Heteropoly Acid Catalysts[J] " Chinese Journal of Chemical Engineering, 2007,15 (6) 895-898.In the present invention, the molar ratio of the phosphorus of phosphorus molybdenum vanadium heteropolyacid, molybdenum, content of vanadium is, P: Mo: V=1: 9-11: 1-3.
During with synthetic 3, the 3-diethoxy propionitrile of processing method of the present invention, owing to having utilized catalyst to adopt the measure of compressive reaction simultaneously, greatly shorten the reaction times, the time has been controlled in 4.0h, thereby has improved reaction efficiency.
Embodiment
Embodiment 1
In HF-100 type autoclave, add 0.20g Palladous chloride-phosphorus molybdenum vanadium heteropolyacid/activated-carbon catalyst, 0.106g (2.0mmol) vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene (interior mark).Then fill oxygen as 2.0MPa, induction stirring, reacts 4.0h at 60 DEG C.After reaction finishes, reactor is placed in to cold hydrazine cooling, then slowly emits oxygen.By reaction liquid, after filtration under diminished pressure, filtrate is used 3*10ml extracted with diethyl ether, combining extraction liquid, and with SP-3420 type gas chromatograph (FID) analysis, gained 3,3-diethoxy propionitrile productive rate is 98%.
Embodiment 2
In HF-100 type autoclave, add 0.20g catalyzer, 0.106g (2.0mmol) vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene.Then fill oxygen to 2.0MPa, induction stirring, reacts 4.0h at 50 DEG C.All the other operation stepss are the same, gained 3, and 3-diethoxy propionitrile and 3-ethoxy propylene nitrile productive rate are respectively 62% and 13%.
Embodiment 3
In HF-100 type autoclave, add 0.20g catalyzer, 0.106g (2.0mmol) vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene.Then fill oxygen as 2.0MPa, induction stirring, reacts 4.0h at 70 DEG C.All the other operation stepss are the same, and gained productive rate is 98%.
Embodiment 4
In HF-100 type autoclave, add 0.20g catalyzer, 0.106g (2.0mmol) vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene.Then fill oxygen as 2.0MPa, induction stirring, reacts 4.0h at 80 DEG C.All the other operation stepss are the same, gained 3, and 3-diethoxy propionitrile and 3-ethoxy propylene nitrile productive rate are respectively 86% and 13%.
Embodiment 5
In HF-100 type autoclave, add 0.20g catalyzer, 0.106g (2.0mmol) vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene.Then fill oxygen as 2.0MPa, induction stirring, reacts 4.0h at 90 DEG C.All the other operation stepss are the same, gained 3, and 3-diethoxy propionitrile and 3-ethoxy propylene nitrile productive rate are respectively 28% and 2%.
Embodiment 6
In HF-100 type autoclave, add 0.20g catalyzer, 0.106g (2.0mmol) vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene.Then fill oxygen as 0.5MPa, induction stirring, reacts 4.0h at 60 DEG C.All the other operation stepss are the same, gained 3, and 3-diethoxy propionitrile and 3-ethoxy propylene nitrile productive rate are respectively 88% and 6%.
Embodiment 7
In HF-100 type autoclave, add 0.20g catalyzer, 0.106g (2.0mmol) vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene.Then fill oxygen as 1.0MPa, induction stirring, reacts 4.0h at 60 DEG C.All the other operation stepss are the same, gained 3, and 3-diethoxy propionitrile and 3-ethoxy propylene nitrile productive rate are respectively 91% and 5%.
Embodiment 8
In HF-100 type autoclave, add 0.20g catalyzer, 0.106g (2.0mmol) vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene.Then fill oxygen as 1.5MPa, induction stirring, reacts 4.0h at 60 DEG C.All the other operation stepss are the same, gained 3, and 3-diethoxy propionitrile and 3-ethoxy propylene nitrile productive rate are respectively 93% and 6%.
Embodiment 9
In HF-100 type autoclave, add 0.20g catalyzer, 0.106g (2.0mmol) vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene.Then fill oxygen as 2.5MPa, induction stirring, reacts 4.0h at 60 DEG C.All the other operation stepss are the same, gained 3, and 3-diethoxy propionitrile and 3-ethoxy propylene nitrile productive rate are respectively 91% and 7%.
Embodiment 10
In HF-100 type autoclave, add 0.20g catalyzer, 0.106g (2.0mmol) vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene.Then fill oxygen as 2.0MPa, induction stirring, reacts 0.5h at 60 DEG C.All the other operation stepss are the same, gained 3, and 3-diethoxy propionitrile and 3-ethoxy propylene nitrile productive rate are respectively 60% and 12%.
Embodiment 11
In HF-100 type autoclave, add 0.20g catalyzer, 0.106g (2.0mmol) vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene.Then fill oxygen as 2.0MPa, induction stirring, reacts 1.0h at 60 DEG C.All the other operation stepss are the same, gained 3, and 3-diethoxy propionitrile and 3-ethoxy propylene nitrile productive rate are respectively 85% and 5%.
Embodiment 12
In HF-100 type autoclave, add 0.20g catalyzer, 0.106g (2.0mmol) vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene.Then fill oxygen as 2.0MPa, induction stirring, reacts 2.0h at 60 DEG C.All the other operation stepss are the same, gained 3, and 3-diethoxy propionitrile and 3-ethoxy propylene nitrile productive rate are respectively 87% and 5%.
Embodiment 13
In HF-100 type autoclave, add 0.20g catalyzer, 0.106g (2.0mmol) vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene.Then fill oxygen as 2.0MPa, induction stirring, reacts 3.0h at 60 DEG C.All the other operation stepss are the same, gained 3, and 3-diethoxy propionitrile and 3-ethoxy propylene nitrile productive rate are respectively 91% and 6%.
The molar ratio of phosphorus in the phosphorus molybdenum vanadium heteropolyacid in catalyzer used in the present invention, molybdenum, content of vanadium is, P: Mo: V=1: 9-11: 1-3.Adopt respectively phosphoric acid, molybdic oxide and Vanadium Pentoxide in FLAKES be as phosphorus source, He Fan source, molybdenum source.
The preparation method of phosphorus molybdenum vanadium heteropolyacid is as follows:
First, get the each 0.30mol of molybdic oxide and Vanadium Pentoxide in FLAKES and be dispersed in 100ml deionized water, mixture is heated to 100 DEG C of back flow reaction; Then, adding content is 85% phosphoric acid solution 0.20ml, continues after back flow reaction 24h, to obtain the brick red solution of clarification at this temperature.Finally, by prepared solution recrystallization three times at 5 DEG C, crystalline material, through drying treatment, obtains required phosphorus molybdenum vanadium heteropolyacid finished product.
The preparation of Palladous chloride/phosphorus molybdenum vanadium heteropolyacid catalyzer: the Palladous chloride of getting 0.4mmol is dissolved in 20ml deionized water, then add the gac of 0.8g in palladium chloride solution, after at room temperature stirring dipping 6h, after the phosphorus molybdenum vanadium heteropolyacid that 0.08mmol is prepared as stated above dissolves with 20ml deionization, add in above-mentioned system, continue to stir and spend the night.Finally will flood system after filtration, washing, dry, the solid matter obtaining is required catalyzer finished product.
Claims (4)
1. prepare 3 with catalysis synthesis process for one kind, the method of 3-diethoxy propionitrile, it is characterized in that utilizing the Palladous chloride/phosphorus molybdenum vanadium heteropolyacid being carried on gac is catalyzer, in autoclave reactor, make vinyl cyanide and ethanol generation acetalation, the molar ratio of vinyl cyanide and ethanol is 1: 25～1: 85, temperature of reaction is 50～90 DEG C, and when reaction, oxygen pressure is 0.5～2.5Mpa, and in catalyzer, Palladous chloride molecular formula is: PdCl
2; Phosphorus molybdenum vanadium heteropolyacid molecular formula is: H
3+npMo
12-nv
no
40, n=1-3.
2. according to claim 1ly prepare 3 with catalysis synthesis process, the method of 3-diethoxy propionitrile, it is characterized in that reaction conditions is: the Palladous chloride/phosphorus molybdenum vanadium heteropolyacid catalyzer that adds 0.2g, 2.0mmol vinyl cyanide, 5.0ml ethanol, 0.10ml chlorobenzene, oxygen pressure is 2.0MPa, temperature of reaction is 60 DEG C.
3. the catalysis synthesis process described in claim 1 or 2 prepares 3, the method of 3-diethoxy propionitrile, is characterized in that in catalyzer that Palladous chloride and phosphorus molybdenum vanadium heteropolyacid are carried on gac, wherein, palladium content on gac is 2.0-6.6wt.%, and heteropolyacid is 10-20wt%.
4. catalysis synthesis process according to claim 3 is prepared the method for 3,3-diethoxy propionitrile, it is characterized in that the preparation method of Palladous chloride/phosphorus molybdenum vanadium heteropolyacid catalyzer used is as follows:
First take in proportion molybdic oxide and Vanadium Pentoxide in FLAKES and be dispersed in deionized water, be heated to 100 DEG C of backflows; Then, adding content is 85% phosphoric acid solution, continues after back flow reaction 24h, to obtain the brick red solution of clarification at this temperature, and prepared solution is carried out to recrystallization, and crystalline material, through drying treatment, obtains required phosphorus molybdenum vanadium heteropolyacid;
The Palladous chloride of getting 0.4mmol is dissolved in deionized water, then add the gac of 0.8g amount in palladium chloride solution, after at room temperature stirring dipping 6h, the phosphorus molybdenum vanadium heteropolyacid that 0.08mmol is prepared as stated above adds in above-mentioned system after dissolving with 20ml deionization, continues to stir and spends the night, finally will flood system after filtration, washing, dry, the solid matter obtaining is required catalyzer finished product.
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| CN112457215B (en) * | 2020-11-24 | 2022-08-23 | 上海诺哈尔化工技术有限公司 | Synthetic method of 3, 3-dimethoxypropionitrile |
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