CN104387235B - Method for synthesizing prenol employing selective hydrogenation of 3-methylcrotonaldehyde - Google Patents
Method for synthesizing prenol employing selective hydrogenation of 3-methylcrotonaldehyde Download PDFInfo
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- CN104387235B CN104387235B CN201410671165.1A CN201410671165A CN104387235B CN 104387235 B CN104387235 B CN 104387235B CN 201410671165 A CN201410671165 A CN 201410671165A CN 104387235 B CN104387235 B CN 104387235B
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- prenol
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a method for synthesizing prenol employing selective hydrogenation of 3-methylcrotonaldehyde. The method comprises the following steps: feeding, nitrogen and hydrogen substitution, hydrogenation reaction, and separation. The used raw materials comprise 1 part of 3-methylcrotonaldehyde, 0.1-10 parts of water and 0.02-0.2 part of a catalyst; and the used catalyst is a water-soluble complex which is formed by a water-soluble salt of the group VIII metal and a water-soluble ligand. The 3-methylcrotonaldehyde conversion ratio and the selectivity of prenol of the synthetic reaction are high; a water phase of the catalyst can be applied repeatedly for over 20 times; the unit consumption of the catalyst is low; the production cost is greatly reduced; and the method is suitable for industrial production.
Description
Technical field
The present invention relates to the synthetic method of a kind of medicine, spices and pesticide intermediate prenol, specifically a kind of
The method that isoamyl olefine aldehydr selective hydrogenation synthesizes prenol.
Background technology
Prenol（3- methyl-2 butenol）, it is a kind of important medicine, spices and pesticide intermediate, can be used for giving birth to
Produce citral, different vegetable alcohol, DV chrysanthemumic acid methyl esters, vitamin E, vitamin A, carotenoid intermediate etc. it can also be used to other have
Machine synthesizes.
The synthetic method of current prenol mainly has following several：
1st, isobutene method：Patent US4028424 describes to be obtained through prins reaction with isobutene and formaldehyde for raw material different
Pentenol, but this reaction selectivity is poor, and the selectivity of prenol is about 5%, generates 80～90% 3- methyl -3- fourth simultaneously
Enol；
Patent WO2008037693 describes to be obtained 3- methyl -3- butylene for raw material through condensation reaction with isobutene and formaldehyde
Alcohol, then on heterogeneous noble metal catalyst, isomerization generates 3- methyl-2 butenol, this catalysis by 3- methyl -3- butenol
Agent is made up of Pd, Se and Te, and in addition this reaction has 2.5% excessive hydrogenation product isoamyl alcohol to generate；
Patent US4219683 describes to be converted into 3- methyl -3- butenol isomery in the presence of palladium catalyst and hydrogen
Prenol, conversion ratio is 39～54%, selective 82～99%.The shortcoming of this process route is that isobutene and formaldehyde react to be needed
Want HTHP, severe reaction conditions, in addition, the isomerization reaction conversion ratio of 3- methyl -3- butenol is low, separating difficulty is big.
2nd, methyl butenol isomerate process：Under alkalescence condition, acetone and acetylene ethynylation, generate methyl butynol, then
Methyl butenol is obtained with lindlar catalyst hydrogenation, obtains prenol in isomerization.
Describe in patent US3925485 example with 2- methyl -3- butene-2 alcohol（Methyl butenol）For raw material, with positive vanadium
Sour tetrahydrochysene virtue camphor tree ester is catalyst, and 150 DEG C of reaction 7h obtain the conversion ratio 25.6% of prenol, yield can be to 83%；Patent
CN101381283A describes to carry out methyl butenol using one or more of rhenium catalyst, tungsten catalyst and vanadium catalyst
Isomerization reaction, in 130～150 DEG C of temperature, under pressure 0.2～0.3MPa, can continuously obtain prenol, yield is 86～
93%.The shortcoming of above-mentioned two patent techniques is balanced reaction for isomerization reaction, and conversion ratio is low, and separating difficulty is big, and the catalysis using
Agent preparation is difficult, and price is higher.
3rd, isoamyl olefine aldehydr hydrogenation method：Isoamyl olefine aldehydr is carried out selective hydrogenation prenol is obtained.Tomoo et al.（J
Org Chem 1998,63:2378-2381）Using to α, beta-unsaturated carbonyl compound has the Rh of high catalytic activity6
(CO)16It is catalyst with amine substance, with formic acid and isopropanol as hydrogen source, hydrogenation reaction is carried out to isoamyl olefine aldehydr, conversion ratio can
Reach 92%, prenol selective 96%, isoamyl alcohol selectively reaches 4%.Patent US4929776 adopts RuH2(PPh3) it is catalyst,
Isopropyl alcohol and water or toluene make solvent, isoamyl olefine aldehydr at 35～50 DEG C, under 2～3MPa be hydrogenated with, conversion ratio up to 100%, iso-amylene
Alcohol selectively reaches 90%.
Patent CN1258506C and CN1323059C describe to carry out using Ru doping Fe loaded catalyst and Pt/ZnO
The method that corresponding unsaturated alcohol is prepared in olefinic beta-unsaturated carbonyl compounds selective hydrogenation, the selectivity of wherein unsaturated alcohol reaches
More than 90%, saturated alcohols selective 4～6%, but the example of isoamyl olefine aldehydr hydrogenation is not all described.
Isoamyl olefine aldehydr Hydrogenation is in isoamyl olefine aldehydr molecule there is C=C and C=O for its technological difficulties of prenol simultaneously
Key, because C=O bond energy is more than C=C bond energy, and the two has conjugation so that reaction will be hydrogenated with C=O key and not break
Bad C=C key is more difficult, and isoamyl alcohol inevitably in hydrogenation process（Saturated alcohols）Product.
Content of the invention
The technical problem to be solved is to overcome the shortcomings of that above-mentioned prior art exists, and provides a kind of isoamyl olefine aldehydr
Carry out the method that selective hydrogenation synthesizes prenol in water-organic biphasic, realize following goal of the invention：Isoamyl olefine aldehydr converts
The selectivity of rate and prenol is high；Product be can be easily separated with catalyst, easy and simple to handle, energy-saving；Catalyst aqueous phase can be real
The recycled of existing more than 20 times, catalyst consumption is low, significantly reduces production cost, suitable industrialized production.
For solving above-mentioned technical problem, the present invention employs the following technical solutions：
A kind of method that isoamyl olefine aldehydr selective hydrogenation synthesizes prenol, comprises the following steps：Feed intake；Nitrogen, hydrogen
Displacement；Hydrogenation reaction；Separate.
The following is the improvement further to technique scheme：
In described material addition step, the raw material of input is：Isoamyl olefine aldehydr, water and catalyst, wherein catalyst are the VIIIth race's gold
The water soluble complex that the water soluble salt belonging to and water soluble ligand are formed.
The water soluble salt of described group VIII metal is ruthenium acetate, ruthenic chloride, nitric acid ruthenium, rhodium sulfate, radium chloride, nitric acid
One or more of rhodium, acid chloride, palladium bichloride, palladium nitrate, iridium acetate, iridium chloride, nitric acid iridium.
Described water soluble ligand is water-soluble phosphine ligand and water-soluble imine ligand.
The water soluble salt of described group VIII metal and the mass ratio of water soluble ligand are 0.001～0.01:1.
Put into raw material mass ratio be：1 part of isoamyl olefine aldehydr, 0.1～10 part of water and 0.02～0.2 part of catalyst.
In described hydrogenation reaction step, Hydrogen Vapor Pressure 0.5～15.0MPa, 30～150 DEG C of reaction temperature.
In described hydrogenation reaction step, under conditions of speed of agitator 200～1000rpm, compressive reaction 3～30h.
In described hydrogenation reaction step, until isoamyl olefine aldehydr conversion ratio ＞ 98%, stop this reactions steps.
Using the method, conversion ratio >=98% of isoamyl olefine aldehydr, prenol selectivity >=99%, excessive hydrogenation product isoamyl
The selective ＜ 1% of alcohol.
The present invention compared with prior art, has advantages below：
1. reacted using water-organic biphasic, reaction finishes two phase stratification, product can be directly obtained it is easy to product and catalysis
The separation of agent, easy and simple to handle, energy-saving；
2. the water-soluble group VIII metal complex catalysis system using, the choosing of isoamyl olefine aldehydr conversion ratio and prenol
Selecting property is higher, and conversion ratio reaches more than 98%, and prenol selectively reaches more than 99%, the selection of excessive hydrogenation product isoamyl alcohol
Property be less than 1%；
3. catalyst aqueous phase can achieve the recycled of more than 20 times, and catalyst consumption is low, significantly reduces and produces into
This, suitable industrialized production.
With reference to embodiment, technical scheme is described further.
Specific embodiment
A kind of method that isoamyl olefine aldehydr selective hydrogenation synthesizes prenol, comprises the following steps：
A, feed intake
By 1 part of isoamyl olefine aldehydr, 0.1～10 part of water, and the water soluble salt of 0.02～0.2 part of group VIII metal and water solubility
The water soluble complex catalyst that part is formed is added in autoclave.
B, nitrogen, hydrogen exchange
Nitrogen displacement three times, hydrogen exchange three times.
C, hydrogenation reaction
Then in Hydrogen Vapor Pressure 0.5～15.0MPa, 30～150 DEG C of reaction temperature, the bar of speed of agitator 200～1000rpm
Under part, compressive reaction 3～30h, until isoamyl olefine aldehydr conversion ratio ＞ 98%.
D, separation
After reaction terminates, stratification, the aqueous phase containing catalyst continues set and uses lower batch reaction, and organic phase is iso-amylene
Alcohol.
Embodiment 1
By 6g ruthenic chloride and three-（To phenoxy group-APEO）- phosphine complex catalyst, 500g water are added to magnetic
In the 2L autoclave of power stirring and temperature controller, it is subsequently adding 200g isoamyl olefine aldehydr.Ruthenic chloride and three in complex catalyst-（To benzene
Epoxide-APEO）- phosphine mass ratio is 0.009:1.
With nitrogen displacement three times, use hydrogen exchange three times afterwards.
It is heated to 150 DEG C, pressurized with hydrogen to 3.0MPa, 700rpm stirs, and reacts 3 hours, sample analysis isoamyl olefine aldehydr turns
Rate is more than 99%.
It is water-cooled, extrude reactant liquor, stratification, the aqueous phase containing catalyst can continue set and use lower batch reaction, organic
It is mutually prenol.
Through gas chromatographic analysis, the conversion ratio of isoamyl olefine aldehydr is 99.98%, prenol selective 99.10%.
Embodiment 2
25g rhodium nitrate and triphenylphosphine sodium sulfonate complex catalyst, 200g water are added to magnetic agitation and temperature control
In the 2L autoclave of device, it is subsequently adding 300g isoamyl olefine aldehydr.Complex catalyst rhodium nitrate and the mass ratio of triphenylphosphine sodium sulfonate
For 0.001:1.
With nitrogen displacement three times, use hydrogen exchange three times afterwards.
It is heated to 30 DEG C, pressurized with hydrogen to 5.0MPa, 700rpm stirs, and reacts 28 hours, sample analysis isoamyl olefine aldehydr turns
Rate is more than 98%.
It is water-cooled, extrude reactant liquor, stratification, the aqueous phase containing catalyst can continue set and use lower batch reaction, organic
It is mutually prenol.
Through gas chromatographic analysis, the conversion ratio of isoamyl olefine aldehydr is 98.15%, prenol selective 99.20%.
Embodiment 3
By 25g rhodium nitrate and three-（To phenoxy group-APEO）- phosphine complex catalyst, 800g water are added to magnetic
In the 2L autoclave of power stirring and temperature controller, it is subsequently adding 100g isoamyl olefine aldehydr.Rhodium nitrate and three in complex catalyst-（To benzene
Epoxide-APEO）The mass ratio of-phosphine is 0.01:1.
With nitrogen displacement three times, use hydrogen exchange three times afterwards.
It is heated to 100 DEG C, pressurized with hydrogen to 0.5MPa, 500rpm stirs, and reacts 18.5 hours, sample analysis isoamyl olefine aldehydr
Conversion ratio is more than 98%.
It is water-cooled, extrude reactant liquor, stratification, the aqueous phase containing catalyst can continue set and use lower batch reaction, organic
It is mutually prenol.
Through gas chromatographic analysis, the conversion ratio of isoamyl olefine aldehydr is 98.05%, prenol selective 99.40%.
Embodiment 4
20g palladium sulfate and three-(4- methoxyl group -3- sodium sulfonate phenyl) phosphine complex catalysts, 1000g water are added to and carry
In the 2L autoclave of magnetic agitation and temperature controller, it is subsequently adding 250g isoamyl olefine aldehydr.Palladium bichloride and three-(4- in complex catalyst
Methoxyl group -3- sodium sulfonate phenyl) phosphine mass ratio be 0.006:1.
With nitrogen displacement three times, use hydrogen exchange three times afterwards.
It is heated to 130 DEG C, pressurized with hydrogen to 2.0MPa, 1000rpm stirs, and reacts 20 hours, sample analysis isoamyl olefine aldehydr
Conversion ratio is more than 99%.
It is water-cooled, extrude reactant liquor, stratification, the aqueous phase containing catalyst can continue set and use lower batch reaction, organic
It is mutually prenol.
Through gas chromatographic analysis, the conversion ratio of isoamyl olefine aldehydr is 99.05%, prenol selective 99.01%.
Embodiment 5
2g radium chloride and three-(2- methoxyl group -3- sodium sulfonate phenyl) phosphines, 1000g water are added to magnetic agitation and
In the 2L autoclave of temperature controller, it is subsequently adding 100g isoamyl olefine aldehydr.Rhodium sulfate and three-(2- methoxyl group -3- sulphur in complex catalyst
Sour sodium phenyl) phosphine mass ratio be 0.001:1.
With nitrogen displacement three times, use hydrogen exchange three times afterwards.
It is heated to 130 DEG C, pressurized with hydrogen to 10.0MPa, 1000rpm stirs, and reacts 19 hours.Sample analysis isoamyl olefine aldehydr
Conversion ratio is more than 90%.
It is water-cooled, extrude reactant liquor, stratification, the aqueous phase containing catalyst can continue set and use lower batch reaction, organic
It is mutually prenol.
Through gas chromatographic analysis, the conversion ratio of isoamyl olefine aldehydr is 98.11%, prenol selective 99.37%.
Embodiment 6
By 20g palladium bichloride and the complexing of 5- [1- (2,6- diisopropyl phenyl imido)-ethyl] -2- furane sulfonic acid triethyl ammonium
Catalyst, 600g water are added in the 2L autoclave with magnetic agitation and temperature controller, are subsequently adding 300g isoamyl olefine aldehydr.Complexing
The mass ratio of palladium bichloride and 5- [1- (2,6- diisopropyl phenyl imido)-ethyl] -2- furane sulfonic acid triethyl ammonium in catalyst
For 0.008:1.
With nitrogen displacement three times, use hydrogen exchange three times afterwards.
It is heated to 100 DEG C, pressurized with hydrogen to 2.0MPa, 1000rpm stirs, and reacts 9 hours.Sample analysis isoamyl olefine aldehydr turns
Rate is more than 98%,
It is water-cooled, extrude reactant liquor, stratification, the aqueous phase containing catalyst can continue set and use lower batch reaction, organic
It is mutually prenol.
Through gas chromatographic analysis, the conversion ratio of isoamyl olefine aldehydr is 98.35%, prenol selective 99.01%.
Embodiment 7
10g iridium chloride and triphenylphosphine sodium sulfonate complex catalyst, 600g water are added to magnetic agitation and temperature control
In the 2L autoclave of device, it is subsequently adding 300g isoamyl olefine aldehydr.The quality of iridium chloride and triphenylphosphine sodium sulfonate in complex catalyst
Than for 0.004:1.
With nitrogen displacement three times, use hydrogen exchange three times afterwards.
It is heated to 70 DEG C, pressurized with hydrogen to 2.5MPa, 1000rpm stirs, and reacts 10 hours.Sample analysis isoamyl olefine aldehydr turns
Rate is more than 98%,.
It is water-cooled, extrude reactant liquor, stratification, the aqueous phase containing catalyst can continue set and use lower batch reaction, organic
It is mutually prenol.
Through gas chromatographic analysis, the conversion ratio of isoamyl olefine aldehydr is 99.93%, prenol selective 99.22%.
The aqueous phase containing catalyst in embodiment 7 is applied mechanically, its experimental result such as following table：
As seen from the above table, the 18 post-reacted selectivity of catalyst recovery and conversion ratio are still higher.
General principle and principal character and the advantages of the present invention of the present invention have been shown and described above.The skill of the industry
The simply explanation it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and specification for the art personnel
The principle of the present invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these
Changes and improvements both fall within scope of the claimed invention.
Claims (1)
1. a kind of isoamyl olefine aldehydr selective hydrogenation synthesize prenol method it is characterised in that：Comprise the following steps：Feed intake；
Nitrogen, hydrogen exchange；Hydrogenation reaction；Separate；
Described material addition step, iridium chloride and triphenylphosphine sodium sulfonate complex catalyst and water is added in autoclave, Ran Houjia
Enter isoamyl olefine aldehydr；
In described complex catalyst, iridium chloride and the mass ratio of triphenylphosphine sodium sulfonate are 0.004:1；
The mass ratio of described complex catalyst, water and isoamyl olefine aldehydr is 1:60:30；
Described nitrogen, hydrogen exchange step, with nitrogen displacement three times, use hydrogen exchange three times afterwards；
Described hydrogenation reaction step, is heated to 70 DEG C, pressurized with hydrogen to 2.5MPa, and 1000rpm stirs, and reacts 10 hours, sampling
Analysis isoamyl olefine aldehydr conversion ratio is more than 98%；
Described separating step, is water-cooled, extrude reactant liquor, stratification, the aqueous phase containing catalyst can continue set use down criticize
Reaction, organic phase is prenol.
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| CN107089900B (en) * | 2017-04-28 | 2020-06-26 | 山东新和成药业有限公司 | Preparation method of β -phenethyl alcohol |
| CN110643556A (en) * | 2019-08-23 | 2020-01-03 | 浙江工业大学 | Recombinant genetic engineering bacterium for co-expressing enal reductase and glucose dehydrogenase and application thereof |
| CN114262257B (en) * | 2020-09-16 | 2023-07-14 | 万华化学集团股份有限公司 | Method for recycling isoamyl alcohol through citral process waste liquid hydrogenation |
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| US4219677A (en) * | 1976-07-27 | 1980-08-26 | Rhone-Poulenc Industries | Telomerization process |
| FR2623800B1 (en) * | 1987-12-01 | 1990-01-26 | Rhone Poulenc Sante | PROCESS FOR THE PREPARATION OF UNSATURATED ALCOHOLS |
| FR2623799B1 (en) * | 1987-12-01 | 1990-01-26 | Rhone Poulenc Sante | PROCESS FOR THE PREPARATION OF UNSATURATED ALCOHOLS |
| DE102004047836A1 (en) * | 2004-09-29 | 2006-03-30 | Basf Ag | Process for the preparation of optically active 2-methylalkanols |
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