CN108047013A - A kind of synthetic method of isoamyl olefine aldehydr - Google Patents
A kind of synthetic method of isoamyl olefine aldehydr Download PDFInfo
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- CN108047013A CN108047013A CN201711355314.3A CN201711355314A CN108047013A CN 108047013 A CN108047013 A CN 108047013A CN 201711355314 A CN201711355314 A CN 201711355314A CN 108047013 A CN108047013 A CN 108047013A
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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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
- C07C45/66—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
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- 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
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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Abstract
The present invention provides a kind of synthetic method of isoamyl olefine aldehydr, includes the following steps：Epoxy iso-butane is subjected to hydroformylation reaction and obtains hydroxyl isopentyl aldehyde, hydroxyl isopentyl aldehyde is carried out molecule inner dewatering reaction obtains isoamyl olefine aldehydr.The present invention provides a kind of synthetic methods of the isoamyl olefine aldehydr without harsh reaction condition.
Description
Technical field
The present invention relates to the preparing technical field of isoamyl olefine aldehydr, more particularly to a kind of synthetic method of isoamyl olefine aldehydr.
Background technology
Isoamyl olefine aldehydr (- 1 butyraldehyde of 3- methyl -2- alkene) is the pass for preparing vitamin E, vitamin A and fragrance product citral
Key intermediate.In the prior art, generally using isobutene and formaldehyde prins reaction occurs for industrial production to prepare 3- methyl -3-
Alkene-n-butyl alcohol, then double-bond isomerism prepare 3- methyl -2- alkene-n-butyl alcohol, the chosen property oxidation again of 3- methyl -2- alkene-n-butyl alcohol
Prepare isoamyl olefine aldehydr.Prins reaction in this synthetic route between isobutene and formaldehyde will be in hyperpressure hyperthermal (such as 250
DEG C, 250Bar pressure) harsh conditions under carry out；Isomerization reaction to use noble metal catalyst under harsh restrictive condition into
Row.In addition, there is, oxidation product complexity, by-product high to catalyst requirement in oxidation reaction of the prenol to isoamyl olefine aldehydr
More, the problems such as separation is difficult.In addition, the industrial product route of existing isoamyl olefine aldehydr also there are commercial plant investment it is huge, production
Product yield is high, the technical issues of of need to continuing to obtain improvement such as with high costs.
It is well known that epoxide is a kind of important basic chemical industry raw material, due to the presence of intramolecular ring strain, make
There is very high reactivity into this kind of compound, be widely used in the fields such as petrochemical industry, fine chemistry industry and organic synthesis.One
Under fixed reaction condition, open loop carbonylation can occur for epoxide.It is anti-in low-carbon epoxy compound compound carbonylation open loop
Ying Zhong, hydroformylation reaction are always the hot spot studied, it provides a kind of cheap approach to prepare beta-hydroxy aldehyde.Such as
In technology disclosed in CN94191112, CN95195314, ethylene oxide prepares beta-hydroxy aldehyde, Ran Houtong by hydroformylation reaction
It crosses after hydrogenation and obtains the technique of 1,3- propylene glycol and have been carried out industrializing.Beta-hydroxy aldehyde has polyfunctional group, can derive
A variety of functional compounds.The hydroformylation reaction of low-carbon epoxides provides a new potential road for industrial quarters
Line.But it is more than propylene, the hydroformylation reaction difficulty of the epoxide of substituted base dramatically increase, and because epoxy
Compound property is more active, is often accompanied with the generation of some side reactions during the reaction, such as isomerization, carbonyl functional group
Reduction hydrogenation, the dimerization etc. of beta-hydroxy aldehyde.The epoxide for also rarely having more than on propylene, substituted base at present passes through
Hydroformylation reaction come prepare corresponding aldehyde industrialization successful application Case Report.
For the industrial product route of existing isoamyl olefine aldehydr, there are product is complicated, by-product is more, product yield is not high, reaction
A kind of new isoamyl olefine aldehydr synthetic route, the face to solve urgently are developed in the key technical problems such as harsh, with high costs, this field
The technical barrier faced.
The content of the invention
The present invention provides a kind of isoamyl olefine aldehydr without harsh reaction condition to solve problems of the prior art
Synthetic method.
For the present invention to reach its purpose, the technical solution of use is as follows：
The present invention provides a kind of synthetic method of isoamyl olefine aldehydr, includes the following steps：Epoxy iso-butane is subjected to hydrogen formyl
Change reaction and obtain hydroxyl isopentyl aldehyde, hydroxyl isopentyl aldehyde is carried out molecule inner dewatering reaction obtains the isoamyl olefine aldehydr.
The synthetic method of the present invention, it is preferred that the hydroformylation reaction carries out in the presence of a catalyst, the catalyst
Including rhodium compound and organophosphor ligand.Using rhodium compound and organophosphor ligand combination application, the network of organophosphor and rhodium ion
Cooperation, which is used, preferably to play coordinative role with rhodium ion, and improves the stability of rhodium catalyst.It is it is further preferred that described
The amount ratio of the substance of rhodium compound and organophosphor ligand is 1:10~1000, more preferable 50-500.Preferably, compared with hydrogen formyl
Change the reaction system gross mass of reaction, the dosage of rhodium compound is 0.01%~1% in the catalyst, preferably 0.02-0.1%
To obtain preferable catalytic effect.
The synthetic method of the present invention, it is preferred that the rhodium compound is selected from Rh (CO)2(acac)、RhCl3·3H2O、RhCl
(CO)2、Rh4(CO)12、Rh6(CO)16(RhNO3)3In one or more.Using preferred rhodium compound and organophosphor ligand
Combination application can be avoided preferably using other metallic catalysts common condensation, hydrogenation of isomery, aldehyde of epoxides etc.
Side reaction significantly improves yield, and the rhodium compound more preferably used is Rh (CO)2(acac)。
The present invention synthetic method, it is preferred that the organophosphor ligand can be selected from trialkyl phosphine, aryl phosphine, amino phosphine,
One or more in carboxyl phosphine and organic phosphite, the organic phosphite are selected from single organic phosphite, double organic
One or more in phosphite ester, three organic phosphites.Using preferred organophosphor ligand, with rhodium metal compound group
It closes, particularly with preferred rhodium metal compound combination application, the activity of catalyst and the selectivity of reaction can be promoted.One
In kind preferred embodiment, the trialkyl phosphine can be preferably that its alkyl is the alkyl containing 4~12 carbon, which can be
Cycloalkyl.
The synthetic method of the present invention, it is preferred that the organophosphor ligand is organic phosphite, and further preferably three have
Machine phosphite ester.It is furthermore preferred that the organic phosphite is three (substitution alkyl) phenyl phosphites.Still more preferably have
Just like three (substitution alkyl) phenyl phosphites of lower structure formula (I)：
Wherein, the R in formula (I)1-R3It is independently selected from straight chained alkyl, the branched alkyl of C3~C10 of H, C1~C10
Or the cycloalkyl of carbon number≤10.It is preferred that using the organic phosphite with structure formula (I) as having in catalyst
Machine phosphorus ligand has the characteristics that the hyper-branched raising spent, can promote catalytic activity.
The synthetic method of the present invention, it is preferred that the organic phosphite is selected from triphenyl phosphite, three (the tertiary fourths of 2-
Base -4- aminomethyl phenyls) phosphite ester, three (2,4- di-t-butyl -6- aminomethyl phenyls) phosphite esters, three (2- methyl-6-tert butyl
Phenyl) phosphite ester, three (2,4- di-tert-butyl-phenyls) phosphite esters, one in three (2,6- di-tert-butyl-phenyls) phosphite esters
Kind is a variety of.Shown in three its structural formula of (2,6- di-tert-butyl-phenyls) phosphite ester such as following formulas (II)：
The synthetic method of the present invention, it is preferred that the hydroformylation reaction carries out in the presence of co-catalyst, and described help is urged
Agent is nitrogenous organic compound, using nitrogenous organic compound as co-catalyst, can improve epoxy ring opening reaction
Selectivity, carbonyl is made to be more likely to from the smaller position attack epoxide ring of steric hindrance.The co-catalyst is preferably selected from ethanolamine
One or more in class compound, imidazoles and imidazole derivative or pyridine and pyridine derivate.It is further preferred that institute
State co-catalyst be selected from 3- pyridones, 2- (dimethylaminomethyl) -3- pyridones, imidazoles, ethanolamine, diethanol amine,
One or more in triethanolamine, the co-catalyst are more preferably 2- (dimethylaminomethyl) -3- pyridones, 3- hydroxyls
One kind in yl pyridines and imidazoles or at least two.It is further preferred that the reaction system gross mass based on hydroformylation reaction,
The dosage of the co-catalyst is 5%~50%, preferably 10%~20%.
The synthetic method of the present invention, it is preferred that the hydroformylation reaction carries out in the presence of polar organic solvent, described
Polar organic solvent preferably includes the tert-butyl alcohol, cyclohexanol, dimethyl ether, diethyl ether, glycol dimethyl ether, methyl tertiary butyl ether(MTBE), second
Base tertbutyl ether, tetraethylene glycol methyl ether, polyoxyethylene alkylphenol ether, tetrahydrofuran, dimethoxy-ethane, methyl iso-butyl ketone (MIBK) and
One or more in isophorone.More preferably polyoxyethylene alkylphenol ether, the polyoxyethylene alkylphenol ether are preferred
For (C4~C16) alkylphenol polyoxyethylene ether, more preferably octyl phenol polyoxyethylene ether.The introducing of polyoxyethylene ether group can be with
It provides to synthesis gas (CO/H2) superior solubility property, and the introducing of preferred chain alkyl can increase hydroformylation and have
Machine substrate is in the exposure level of the solubility of system, increase organic substrates and synthesis gas, raising reaction efficiency.
The synthetic method of the present invention, it is preferred that the epoxy iso-butane is with containing CO and H2Gas haptoreaction occur
The hydroformylation reaction.
The synthetic method of the present invention, it is preferred that the condition of the hydroformylation reaction includes：Temperature is 20-200 DEG C, pressure
Power is 1-20MPa, CO and H2Molar ratio be 1:5-5:1；It is further preferred that temperature is 50-150 DEG C, pressure 3-
10MPa, CO and H2Molar ratio be 1:2-2:1.
The synthetic method of the present invention, it is preferred that the molecule inner dewatering reaction is in no catalyst or has depositing for catalyst
Carry out.It is dehydrated in the presence of a catalyst, can promote dehydration, the catalyst is preferably selected from sulfuric acid, phosphoric acid, right
One or more in toluenesulfonic acid, solid acid catalyst, the solid acid catalyst are, for example, acid-exchange resin, divide
One or more in sub- sieve, heteropoly acid etc..The dosage of catalyst is preferably to be dehydrated reaction raw materials gross mass used
0.1%-20%.In the synthetic method of the present invention, the molecule of hydroxyl isopentyl aldehyde is carried out more preferably under conditions of no catalyst
Interior dehydration carries out direct thermal cracking in the condition of no catalyst, avoids using aldehyde radical pair caused by catalyst (such as strong acid)
The generation of reaction and it can avoid the problem that reaction to the corrosion of equipment material and thus three-protection design for triggering etc..Preferably,
When carrying out the intramolecular dehydration in the absence of a catalyst, the hydroxyl isopentyl aldehyde carries out thermal cracking under the following conditions
The isoamyl olefine aldehydr is made：Temperature is 100-300 DEG C, pressure 1-10BarA, when the reaction time is 120 small；Preferably, temperature
For 150-250 DEG C, pressure 1-5BarA, when the reaction time is 2-10 small.The dehydration is carried out in the presence of having catalyst
When, preferably carry out under the following conditions：Temperature is 50-300 DEG C, pressure 1-10BarA, when the reaction time is 0.1-10 small；It is excellent
Choosing, temperature is 100-200 DEG C, pressure 1-5BarA, when the reaction time is 0.2-5 small.In specific implementation process, preferably
Using means such as reactive distillations, the water of generation is timely deviate from into reaction system, so as to promote chemical balance, is further improved anti-
Answer yield.
The synthetic method of the present invention, it is preferred that further include following steps：Using the material containing isobutene as raw material, with mistake
Oxide occurs epoxidation reaction and the epoxy iso-butane is made.It is further preferred that the ring occurs in the presence of a catalyst
Oxidation reaction.In order to obtain higher reaction yield, the molybdenum salt that the chemical valence that the catalyst is preferably selected from molybdenum is 4-6, into one
Step is preferably selected from MoO3、Mo(CO)5、MoCl5、MoO2(acac)2In one or more, more preferably MoO2(acac)2,
Acac refers to levulinic ketone group, and the introducing of organic coordination group can improve the contact effect of reaction raw materials, significant to improve instead
Answer efficiency.Preferably, the reaction system gross mass based on epoxidation reaction, the catalyst amount are 0.01%~0.1%.Institute
The reaction condition for stating epoxidation reaction preferably includes：Temperature is 20-200 DEG C, pressure 0.1-10MPa, reaction time 1-20
Hour, the amount ratio of the substance of the peroxide and isobutene is 1:2-2:1；It is further preferred that temperature is 50-150 DEG C, pressure
Power is 0.5-5MPa, when the reaction time is 2-10 small.Preferably, the peroxide includes hydrogen peroxide, peroxide vinylbenzene, mistake
One or more in oxygen cumene, tert-butyl hydroperoxide and peroxy acid, more preferably tert-butyl hydroperoxide.More preferably
A kind of embodiment in, preferably using tert-butyl hydroperoxide as peroxide, with MoO2(acac)2For catalyst, can obtain more
Good reaction yield.
Heretofore described pressure is absolute pressure unless otherwise specified.
For the ease of understanding the synthetic route of the present invention, the key reaction road in a kind of specific embodiment is enumerated below
Line, only a kind of example herein, not to the limitation of the present invention：
Technical solution provided by the invention has the advantages that：
Synthetic method provided by the invention avoids the process conditions of existing commercial routes harshness, can be more mild
Under the conditions of acquisition target product in high yield, and then for isoamyl olefine aldehydr is utilized to synthesize prenol, citral, vitamin A, dimension life
Plain E etc. provides new route selection.
Description of the drawings
Fig. 1 is the mass spectrogram of epoxy iso-butane；
Fig. 2 is the mass spectrogram of isoamyl olefine aldehydr.
Specific embodiment
For a better understanding of the technical solution of the present invention, with reference to the embodiment content that the present invention is further explained,
But present disclosure is not limited only to following embodiment.
Quantitative analysis carries out raw material and product using gas-chromatography in following embodiment or comparative example and and then calculates anti-
Effect is answered, analytical conditions for gas chromatography is as follows：
Chromatographic column：Shimadzu HP-PONA (specification is 50m × 0.2mm × 0.25 μm)；Injector temperature：280℃；Split ratio：
50:1；Column flow：0.5ml/min；Temperature program：40 DEG C of holdings 8min, 10 DEG C/min rise to 240 DEG C；Detector temperature：300
℃；H2Flow：40ml/min；Air mass flow：400ml/min.
Reagent used is described as follows in following embodiment or comparative example：Isobutene, tert-butyl hydroperoxide TBHP come
From ten thousand magnificent Yantai industry parks, purity 99%.Reagent in addition to source is indicated in embodiment, the buying of remaining reagent are tried from Aladdin
Agent, analysis are pure.
Embodiment 1
The present embodiment prepares isoamyl olefine aldehydr and includes the following steps：
(1) epoxy iso-butane is prepared：Into compressive reaction kettle, 150g isobutenes, 1g MoCl are added in5, 5g ethylene glycol,
300g tert-butyl hydroperoxide (TBHP), fills N2To pressure 0.5Mpa, 4h is reacted at 120 DEG C.Product epoxy iso-butane (IBO) is received
Rate 90%.The epoxy iso-butane 172g that rectifying separation obtains purity 99.5% is spare, epoxy iso-butane mass spectrogram such as 1 institute of attached drawing
Show.
(2) the epoxy iso-butane for taking 10g prepared above adds in 500ml stirred under pressure reaction kettles, and 125 DEG C of reaction temperature is closed
Into atmospheric pressure 8MPa, CO：H2Volume ratio (i.e. molar ratio)=2:1, with 0.1gRh (CO)2(acac), the neat Xiang chemical industry life in 10g Zibo
(rhodium compound and organic phosphite rub for catalyst for three (2,4- di-tert-butyl-phenyls) phosphite esters (purity 98%) of production
Er Biyue 1:40) co-catalyst, is not added, with 150g octyl phenol polyoxyethylene ether (CAS：It is 9036-19-5) solvent, reaction
24h.Epoxy iso-butane conversion ratio about 45%, hydroxyl isopentyl aldehyde selectivity about 70%, the nuclear-magnetism result of hydroxyl isopentyl aldehyde：1H NMR
(400MHz,CDCl3) δ 1.24 (s, 6H) 2.07 (d, J=6.20Hz, 2H) 3.65 (s, 1H) 5.02-5.07 (m, 2H) 5.82 (m,
1H)。
(3) reaction kettle in (2) is depressurized to normal pressure, uses N2Reaction solution is distilled Removal of catalyst and not turned by displacement 3 times
The raw material of change.The product mixture 8g of acquisition is added in into 150ml three-necked flasks, the A-45 strong acidic ions of 20gDow companies exchange
Resin is catalyst, and 50g hexamethylenes above put the condenser pipe with recirculated cooling water, water knockout drum as water entrainer, normal pressure, 120 DEG C
5h is heated to reflux in oil bath, take kettle liquid carry out GC analyses, hydroxyl isopentyl aldehyde conversion ratio 90%, isoamyl olefine aldehydr selectivity 65%, it is different
The mass spectrogram of pentenals is as shown in Figure 2.
Embodiment 2
The present embodiment prepares isoamyl olefine aldehydr and includes the following steps：
(1) step is the same as (1) the step of embodiment 1；
(2) step is substantially identical with the step (2) in embodiment 1, difference be the present embodiment the step of in (2) plus
Enter 2- (dimethylaminomethyl) -3- pyridones 20g for co-catalyst.The epoxy iso-butane conversion ratio 71% of step (2), hydroxyl
Base isopentyl aldehyde selectivity about 76%.
(3) the step of the present embodiment (3) and (3) are essentially identical the step of embodiment 1, difference is, the present embodiment 2g
P-methyl benzenesulfonic acid replaces the strong-acid ion exchange resin in embodiment 1 as catalyst, heating reaction, reflux 3h at 120 DEG C.It is logical
Cross GC analyses, hydroxyl isopentyl aldehyde conversion ratio 87%, isoamyl olefine aldehydr selectivity 63%.
Embodiment 3
The present embodiment prepares isoamyl olefine aldehydr and includes the following steps：
(1) epoxy iso-butane is prepared：Into compressive reaction kettle, 150g isobutenes, 0.1gMoO are added in2(acac)2, 10g second
Glycol, 170g tert-butyl hydroperoxide (TBHP), fills N2To pressure 2Mpa, 4h is reacted at 90 DEG C.Product epoxy iso-butane (IBO)
Yield 96%.The epoxy iso-butane 130g that rectifying separation obtains purity 99.5% is spare.
(2) 2,6- DI-tert-butylphenol compounds 20g is added in into reaction kettle, the condenser pipe with circulating condensing water, heating is housed on kettle
Reaction temperature control is at 190~200 DEG C after melting, and logical N2Bubbling operates, and is slowly added to phosphorus trichloride 50g dropwise with stirring
(being dripped off in 1h) is reacted；The reaction was continued after adding 3h.After the completion of reaction, removed three times with each 40g ethyl alcohol washing reaction liquid
Unreacted 2,6- DI-tert-butylphenol compounds are removed, then phosphorus trichloride and hydrogen chloride are removed three times with each 40g water washings.Gained is produced
Object is dissolved in 50g glycol dimethyl ethers, evaporative crystallization, filtering, recrystallizes three (2,6- di-tert-butyls of acquisition three times repeatedly
Base) phosphite ester finished product 8g, it is spare to repeat above operation preparation 30g finished products.Three (2,6- di-tert-butyl-phenyls) phosphite esters
Nuclear-magnetism result：1H NMR(400MHz,CDCl3)δ1.35(s,54H)7.07-7.09(m,9H)。
(3) the epoxy iso-butane for taking 10g prepared above adds in 500ml stirred under pressure reaction kettles, and 125 DEG C of reaction temperature is closed
Into atmospheric pressure 18MPa, CO：H2Volume ratio (i.e. molar ratio)=2:1, with 0.1gRh (CO)2(acac), (the bis- tertiary fourths of 2,6- of 30g tri-
Base phenyl) phosphite ester be the catalyst (molar ratio of rhodium compound and organic phosphite about 1:120), 2- (dimethyl amidos
Methyl) -3- pyridones 20g be co-catalyst, with 150g octyl phenol polyoxyethylene ether (CAS：It is 9036-19-5) solvent, instead
It should for 24 hours.Epoxy iso-butane conversion ratio about 65%, hydroxyl isopentyl aldehyde selectivity about 85%.
(4) reaction kettle in (3) is depressurized to normal pressure, uses N2Reaction solution is distilled Removal of catalyst and not turned by displacement 3 times
The raw material of change.The product mixture 8g of acquisition is added in into 150ml three-necked flasks, 50g hexamethylenes above put band Xun Huan as water entrainer
Condenser pipe, the water knockout drum of cooling water are heated to reflux 5h in normal pressure, 170 DEG C of oil baths, and kettle liquid is taken to carry out GC analyses, hydroxyl isoamyl
Aldehyde conversion ratio>80%, isoamyl olefine aldehydr selectivity>85%.
By embodiment 1 and embodiment 2 as it can be seen that when epoxy iso-butane progress hydroformylation reaction prepares hydroxyl isopentyl aldehyde,
Addition co-catalyst is significantly improved than not adding co-catalyst, the conversion ratio and selectivity of gained target product.From with
Upper embodiment is as it can be seen that in the molecule in dehydration, without using the selective higher of target product obtained by catalyst.From above reality
Example is applied as it can be seen that the catalyst system combined using rhodium compound of the present invention and organophosphor ligand, hydrogen first is carried out in epoxy iso-butane
When acylation reaction prepares hydroxyl isopentyl aldehyde, selectivity reaches more than 70%, and all obtains preferable conversion ratio, and using three
Embodiment 3 of (2, the 6- di-tert-butyl-phenyl) phosphite ester as organophosphor ligand, it is better, while obtain higher conversion
Rate and selectivity.By above example as it can be seen that the synthesis path for preparing isoamyl olefine aldehydr of the present invention, required reaction condition temperature
With, and with higher conversion ratio and target product selectivity, thus also there is higher product yield.
It will be understood by those skilled in the art that under the introduction of this specification, the present invention can be made some modifications or
Adjustment.These modifications or adjustment should also be as within the scope of the claims in the present invention.
Claims (10)
1. a kind of synthetic method of isoamyl olefine aldehydr, which is characterized in that include the following steps：Epoxy iso-butane is subjected to hydroformylation
Reaction obtains hydroxyl isopentyl aldehyde, and hydroxyl isopentyl aldehyde is carried out molecule inner dewatering reaction obtains isoamyl olefine aldehydr.
2. synthetic method according to claim 1, which is characterized in that the hydroformylation reaction in the presence of a catalyst into
Row, the catalyst include rhodium compound and organophosphor ligand；
Preferably, the amount ratio of the substance of the rhodium compound and organophosphor ligand is 1:10~1000, preferably 1：50~500；
Preferably, compared with the reaction system gross mass of hydroformylation reaction, the dosage of rhodium compound is in the catalyst
0.01%~1%.
3. synthetic method according to claim 2, which is characterized in that the rhodium compound is selected from Rh (CO)2(acac)、
RhCl3·3H2O、RhCl(CO)2、Rh4(CO)12、Rh6(CO)16(RhNO3)3In one or more.
4. according to claim 2-3 any one of them synthetic methods, which is characterized in that the organophosphor ligand is selected from trialkyl
One or more in phosphine, aryl phosphine, amino phosphine, carboxyl phosphine and organic phosphite, the organic phosphite, which is selected from, singly to be had
One or more in machine phosphite ester, double organic phosphites, three organic phosphites.
5. synthetic method according to claim 4, which is characterized in that the organophosphor ligand is organic phosphite；
Preferably, the organic phosphite be three organic phosphites, further preferred three (substitution alkyl) phenylphosphonous acid
Ester；Still more preferably there are three (substitution alkyl) phenyl phosphites of following structure formula (I)：
Wherein, the R in formula (I)1-R3Be independently selected from the straight chained alkyl of H, C1~C10, the branched alkyl of C3~C10 or
The cycloalkyl of carbon number≤10；
Preferably, the organic phosphite is selected from triphenyl phosphite, three (2- tertiary butyl -4- aminomethyl phenyls) phosphorous acid
Ester, three (2,4- di-t-butyl -6- aminomethyl phenyls) phosphite esters, three (2- methyl-6-tert butyl phenyl) phosphite esters, three (2,
4- di-tert-butyl-phenyls) phosphite ester, the one or more in three (2,6- di-tert-butyl-phenyls) phosphite esters.
6. according to claim 2-5 any one of them synthetic methods, which is characterized in that the hydroformylation reaction is in co-catalysis
It is carried out in the presence of agent, the co-catalyst is nitrogenous organic compound, is preferably selected from alcohol amine compound, imidazoles and imidazoles
One or more in analog derivative or pyridine and pyridine derivate；
It is further preferred that the co-catalyst is selected from 3- pyridones, 2- (dimethylaminomethyl) -3- pyridones, miaow
One or more in azoles, ethanolamine, diethanol amine, triethanolamine；
Preferably, the reaction system gross mass based on hydroformylation reaction, the dosage of the co-catalyst is 5%~50%, excellent
Select 10%~20%.
7. according to claim 1-6 any one of them synthetic methods, which is characterized in that the hydroformylation reaction has in polarity
It is carried out in the presence of solvent, the polar organic solvent includes the tert-butyl alcohol, cyclohexanol, dimethyl ether, diethyl ether, glycol dinitrate
Ether, methyl tertiary butyl ether(MTBE), ethyl tert-butyl ether (ETBE), tetraethylene glycol methyl ether, polyoxyethylene alkylphenol ether, tetrahydrofuran, dimethoxy
One or more in ethane, methyl iso-butyl ketone (MIBK) and isophorone；The polyoxyethylene alkylphenol ether be preferably (C4~
C16) alkylphenol polyoxyethylene ether, more preferable octyl phenol polyoxyethylene ether.
8. according to claim 1-7 any one of them synthetic methods, which is characterized in that the epoxy iso-butane with containing CO and
H2Gas haptoreaction the hydroformylation reaction occurs；
Preferably, the condition of the hydroformylation reaction includes：Temperature is 20-200 DEG C, pressure 1-20MPa, CO and H2Rub
You are than being 1:5-5:1；It is further preferred that temperature is 50-150 DEG C, pressure 3-10MPa, CO and H2Molar ratio be 1:2-
2:1。
9. according to claim 1-8 any one of them synthetic methods, which is characterized in that the molecule inner dewatering reaction is not having
Catalyst or the presence for having catalyst carry out；The catalyst is preferably selected from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid and solid acid catalysis
One or more in agent, dosage are preferably the 0.1%-20% of the reaction raw materials gross mass used in molecule inner dewatering reaction；
Preferably, one or more of the solid acid catalyst in acid-exchange resin, molecular sieve and heteropoly acid；
Preferably, when carrying out the molecule inner dewatering reaction in the absence of a catalyst, the hydroxyl isopentyl aldehyde is as follows
Under the conditions of carry out thermal cracking the isoamyl olefine aldehydr is made：Temperature is 100-300 DEG C, pressure 1-10BarA, reaction time 1-
20 it is small when；Preferably, temperature is 150-250 DEG C, pressure 1-5BarA, when the reaction time is 2-10 small；
Preferably, when carrying out the molecule inner dewatering reaction in the presence of having catalyst, carry out under the following conditions：Temperature
For 50-300 DEG C, pressure 1-10BarA, when the reaction time is 0.1-10 small；Preferably, temperature is 100-200 DEG C, and pressure is
1-5BarA, when the reaction time is 0.2-5 small.
10. according to claim 1-9 any one of them synthetic methods, which is characterized in that further include following steps：It is different to contain
The material of butylene is raw material, and epoxidation reaction, which occurs, with peroxide is made the epoxy iso-butane；
Preferably, the epoxidation reaction, the molybdenum that the chemical valence that the catalyst is selected from molybdenum is 4-6 occur in the presence of a catalyst
Salt is preferably selected from MoO3、Mo(CO)5、MoCl5、MoO2(acac)2In one or more；Preferably, based on epoxidation reaction
Reaction system gross mass, the catalyst amount be 0.01%~0.1%；
Preferably, the reaction condition of the epoxidation reaction includes：Temperature is 20-200 DEG C, pressure 0.1-10MPa, during reaction
Between for 1-20 it is small when, the amount of the substance of the peroxide and isobutene is than being preferably 1:2-2:1；Preferably, temperature 50-
150 DEG C, pressure 0.5-5MPa, when the reaction time is 2-10 small；
Preferably, the peroxide include hydrogen peroxide, peroxide vinylbenzene, peroxy isopropyl base benzene, tert-butyl hydroperoxide and
One or more in peroxy acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111484409A (en) * | 2019-01-25 | 2020-08-04 | 新发药业有限公司 | Low-cost preparation method of 2-methyl-4-substituted carbonyloxy-2-butenal |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056678A (en) * | 1990-05-04 | 1991-12-04 | 联合碳化化学品及塑料技术公司 | Be used to produce 1, the catalyzer and the method for 3-glycol and/or 3-hydroxy aldehyde |
| CN1117289A (en) * | 1993-02-05 | 1996-02-21 | 国际壳牌研究有限公司 | Process for making 1,3-diols and 3-hydroxyaldehydes |
| JP2001151764A (en) * | 1999-11-19 | 2001-06-05 | Nof Corp | Method for producing epoxy compound |
| CN101735099A (en) * | 2009-12-18 | 2010-06-16 | 江苏宇翔化工有限公司 | Synthesizing method of S-(+)-2, 2-dimethylcyclopropane carboxamide |
-
2017
- 2017-12-16 CN CN201711355314.3A patent/CN108047013B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056678A (en) * | 1990-05-04 | 1991-12-04 | 联合碳化化学品及塑料技术公司 | Be used to produce 1, the catalyzer and the method for 3-glycol and/or 3-hydroxy aldehyde |
| CN1117289A (en) * | 1993-02-05 | 1996-02-21 | 国际壳牌研究有限公司 | Process for making 1,3-diols and 3-hydroxyaldehydes |
| JP2001151764A (en) * | 1999-11-19 | 2001-06-05 | Nof Corp | Method for producing epoxy compound |
| CN101735099A (en) * | 2009-12-18 | 2010-06-16 | 江苏宇翔化工有限公司 | Synthesizing method of S-(+)-2, 2-dimethylcyclopropane carboxamide |
Non-Patent Citations (1)
| Title |
|---|
| F. GOTTWALT FISCHER: "β-Methyl-acetaldol. (Uber Aldolkondensationen,VI. Mitteilung）", 《AUS D. CHEM. INSTITUT D. UNIVERSITAT WURZBURG》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484409A (en) * | 2019-01-25 | 2020-08-04 | 新发药业有限公司 | Low-cost preparation method of 2-methyl-4-substituted carbonyloxy-2-butenal |
| CN111484409B (en) * | 2019-01-25 | 2023-05-05 | 新发药业有限公司 | Preparation method of 2-methyl-4-substituted carbonyloxy-2-butenal |
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