A method of preparing dihydrocitronellal
阅读说明：本技术 一种制备二氢香茅醛的方法 (A method of preparing dihydrocitronellal ) 是由 于斌成 王联防 董菁 张永振 于 2019-08-30 设计创作，主要内容包括：本发明提供一种制备二氢香茅醛的方法。是以原料柠檬醛作为氢受体,以醇类化合物为氢供体,在催化剂体系作用下发生分子间氢转移反应,得到二氢香茅醛；所述柠檬醛酸值要求小于0.1mgKOH/g；所述催化剂体系包括：非均相镍系催化剂组分包括镍及载体、双金属醇盐。本发明反应压力为常压,反应温度低,易于操控,催化剂价廉易得,产物选择性及原料转化率高,副产品选择性高,能够通过精馏的方式实现二氢香茅醛的轻松分离,方法简单易行,适用于工业化生产。(The present invention provides a kind of method for preparing dihydrocitronellal.It is, using alcohol compound as hydrogen donor, to issue raw intermolecular hydrogen transfer reaction using raw material citral as hydrogen acceptor in catalyst system effect, obtain dihydrocitronellal；The citral acid value requires to be less than 0.1mgKOH/g；The catalyst system includes: that heterogeneous nickel catalyst component includes nickel and carrier, bimetallic alkoxide.Reaction pressure of the present invention is normal pressure, and reaction temperature is low, is easily manipulated, catalyst is cheap and easy to get, and selectivity of product and feed stock conversion are high, and byproduct selectivity is high, the light separation of dihydrocitronellal can be realized by way of rectifying, method is simple and easy, is suitable for industrialized production.)
1. a kind of method for preparing dihydrocitronellal, using alcohol as hydrogen donor, is made using citral as hydrogen acceptor in catalyst system With raw intermolecular hydrogen transfer reaction is issued, dihydrocitronellal is obtained.
2. the method according to claim 1, wherein the citral acid value is less than 0.1mgKOH/g.
3. the method according to claim 1, wherein the catalyst system include heterogeneous nickel catalyst and Bimetallic alkoxide.
4. the method according to claim 1, wherein the heterogeneous nickel catalyst includes carrier loaded Nickel, the carrier include one of active carbon, carbon nanotube, aluminum oxide, silica or a variety of, preferably activity Charcoal；The content of nickel element is 5wt% in the heterogeneous nickel catalyst.
5. the method according to claim 1, wherein the bimetallic alkoxide is Decanol iron cobalt.
6. according to the method described in claim 5, it is characterized in that, the preparation method of the Decanol iron cobalt, including following step Rapid: (1) iron chloride and Decanol react 6-12 hours at 240-280 DEG C, obtain Decanol iron；(2) cobalt chloride and Decanol exist It 240-280 DEG C, reacts 6-12 hours, obtains Decanol cobalt；(3) Decanol iron and Decanol cobalt are at 250-300 DEG C, the reaction time 10-20 hours, obtain Decanol iron cobalt.
7. according to the method described in claim 6, it is characterized in that, the molar ratio of the iron chloride and Decanol is 1:3；It is described The molar ratio of cobalt chloride and Decanol is 1:3；The molar ratio of the Decanol iron and Decanol cobalt is 1:1.
8. method according to claim 1-7, which is characterized in that the dosage of the heterogeneous nickel catalyst with Nickel element quality is calculated as the 0.1~2% of citral quality, and Decanol iron cobalt dosage is the 0.1~0.3% of citral quality.
9. the method according to claim 1, wherein the alcohol include methanol, it is ethyl alcohol, isopropanol, isobutanol, different One of amylalcohol is a variety of；The molar ratio of the alcohol and citral is 2~5:1, preferably 2.4~3.6:1.
10. the method according to claim 1, wherein reaction pressure is normal pressure；Reaction temperature is 30~80 DEG C, It is preferred that 40~60 DEG C；Reaction time is 1~20h, preferably 6~18h.
Technical field
The invention belongs to technical field of organic synthesis, are related to a kind of method for preparing dihydrocitronellal, and in particular to a kind of The method that dihydrocitronellal is prepared by citral.
Background technique
Dihydrocitronellal is a kind of terpenoid, is a kind of organic synthesis intermediate, itself may be used as food industry Fungicide, since the structure of corpus allatum hormone is determined, its application value is further increased.
(the Silca supported ionic liquid catalysts for fine chemical [J] such as Jyri .Appl CatalA:General, 2007,328:68-76.) using ionic liquid and Pd ion-solubility work is carried in acetone Property charcoal cloth on, guarantee citral conversion ratio 100% when, the selectivity of dihydrocitronellal is up to 88%；Pascal etc. (Pressure dependent product distribution of citral hydrogenation over micelle hosted Pd and Ru nanoparticles in supercritical carbon dioxide[J].JCatal, 2006,237:330-336) utilize critical CO2Make solvent, 95 × 105Under the pressure of Pa, it is found that the addition of surfactant makes Pd particle can be uniformly dispersed, and enhance Hydrogenation, and the selectivity for obtaining dihydrocitronellal is 79%.
Above method is that dihydrocitronellal is made by hydrogenation method using noble metal catalyst under citral high temperature and pressure. The method is related to dangerous hydrogenation technique, and temperature, pressure height is harsh to the material of reactor and the substantive requirements of form, your gold catalyst is Metal catalyst is at high cost, and reacts the by-product generation for having excessive hydrogenation or partial hydrogenation, the selectivity of dihydrocitronellal It is low, it is not able to satisfy modern safety high-efficiency environment friendly chemical industry synthesis theory.
S.H.Liu etc. (S.H.Liu, S.Jaenicke, and G.K.Chuah.J.Catal, 2002,206,321-330) It reports after grafting on zirconium iso-propoxide on silica gel, Siliceous MCM-41 and AI-MCM-41 mesopore molecular sieve, is being also with isopropanol Prepared by the cinnamic acid hydrogenation of former agent shows good catalytic activity in the reaction of cinnamyl alcohol.Zhang Yahong etc. (CN106316994A) The lewis acids such as aluminium isopropoxide, zirconium iso-propoxide, ethyl alcohol zirconium, propyl alcohol zirconium are used to realize one step of 5 hydroxymethyl furfural as catalyst It reacts while obtaining the Efficient Conversion of 2,5- furans dicarbaldehyde and 2,5- furyl dimethyl carbinol.
S.H.Liu and Zhang Yahong et al. have used metal-alcoholates mono-salt in an experiment, and good effect is that selectivity adds Hydrogen C=O bond, and to carbon-carbon double bond without reduction effect, and they have used during the reaction and have been not involved in the molten of reaction Agent, the step of increasing post-processing and cost；
Hydrogen transfer reaction is widely used in the reduction of all kinds of unsaturated groups, catalyst type and hydrogen donor type compared with More, the hydrogen transfer reduction of ethylene linkage is the hydrogen transfer reaction defined earliest.Used catalyst is mostly that heterogeneous catalysis is carved, and catalyst is more For Pd/C.
The present invention is directed to realize safe and efficient, the inexpensive preparation of dihydrocitronellal, achieve the purpose that comprehensively utilize raw material.
Summary of the invention
Present invention aims at disadvantages mentioned above existing in the prior art is directed to, a kind of side for preparing dihydrocitronellal is provided Method.Intermolecular hydrogen transfer reaction is realized by the regulation to catalyst system and each component ratio under normal pressure, citral is as hydrogen Receptor realizes selective hydrogenation conversion, and highly selective obtains dihydrocitronellal.The method of the present invention is suitable by selection simultaneously The bimetallic alkoxide added in hydrogen donor compound and catalyst system realizes highly selective hydrogen migration, and obtains high economic valence The target dehydrogenation by-product of value.The dihydrocitronellal and dehydrogenation by-product of the method for the present invention preparation can be realized light by rectifying Separation.
In order to realize the above goal of the invention, The technical solution adopted by the invention is as follows:
A method of dihydrocitronellal being prepared, using citral as hydrogen acceptor, using alcohol as hydrogen donor, in catalyst system Effect issues raw intermolecular hydrogen transfer reaction, obtains dihydrocitronellal.
Citral acid value of the present invention is less than 0.1mgKOH/g.
Catalyst system of the present invention includes heterogeneous nickel catalyst and bimetallic alkoxide.
Heterogeneous nickel catalyst of the present invention includes carrier loaded nickel, and the carrier includes but is not limited to activity Charcoal, carbon nanotube, aluminum oxide, silica, preferably active carbon.
Bimetallic alkoxide of the present invention is Decanol iron cobalt.
The preparation method of Decanol iron cobalt of the present invention, comprising the following steps: (1) iron chloride and Decanol are in 240- It 280 DEG C, reacts 6-12 hours, obtains Decanol iron；(2) cobalt chloride and Decanol are reacted 6-12 hours, are obtained at 240-280 DEG C To Decanol cobalt；(3) at 250-300 DEG C, reaction time 10-20 hour obtains Decanol iron cobalt for Decanol iron and Decanol cobalt.
As a preferred option, it in the preparation method of Decanol iron cobalt of the present invention, is monitored using infrared chromatography anti- It answers.
As a preferred option, in the preparation method of Decanol iron cobalt of the present invention, the step (3) is deposited in solvent It is carrying out, the preferred benzene of solvent.
As a preferred option, in the preparation method of Decanol iron cobalt of the present invention, step (3) reaction terminates Afterwards, low-boiling-point substance is removed by the way of vacuum distillation, obtains Decanol iron cobalt.
The molar ratio of iron chloride and Decanol of the present invention is preferably 1:3.
The molar ratio of cobalt chloride and Decanol of the present invention is preferably 1:3.
The molar ratio of Decanol iron and Decanol cobalt of the present invention is preferably 1:1.
The content of nickel element is 5wt% in heterogeneous nickel catalyst of the present invention.
The dosage of heterogeneous nickel catalyst of the present invention is calculated as the 0.1~2% of citral quality with nickel element quality, Decanol iron cobalt dosage is the 0.1~0.3% of citral quality.
Alcohol of the present invention includes one of methanol, ethyl alcohol, isopropanol, isobutanol, isoamyl alcohol or a variety of, preferably different One of propyl alcohol, isobutanol, isoamyl alcohol are a variety of, more preferably isoamyl alcohol.
Citral is as hydrogen acceptor, including two carbon-carbon double bonds and a C=O bond, by the way that two carbon-carbon double bonds are complete Portion adds hydrogen, and C=O bond is not added hydrogen and prepares dihydrocitronellal, if there is other hydrogenation byproducts to generate in reaction process, can make Ingredient is from difficulty, it is therefore desirable to carry out strict control to hydrogenation selectivity, otherwise be difficult to realize be mass produced.The present invention is to mention High product selectivity realizes the selectivity of two carbon-carbon double bonds using the method for increasing Decanol iron cobalt in catalyst system Add hydrogen.The addition of Decanol iron cobalt can effectively improve the selectivity that citral is hydrogenated to dihydrocitronellal, this is because in alcohol Reduction and heterogeneous nickel catalyst under the action of, it is molten that nickle atom with Decanol iron cobalt forms stable metallic colloid The alcohol of nucleophilicity is converted into the electrophilic aldehyde of height by liquid, the hydrogen adsorbed on alcohol, and then the carbon-carbon double bond of nucleophilicity receives absorption Hydrogen forms stable compound, to show preferable metal collaboration effect to the selective hydrogenation of carbon-carbon double bond in citral It answers.
The molar ratio of hydrogen donor alcohol and citral of the present invention is 2~5:1, preferably 2.4~3.6:1.
Intermolecular hydrogen transfer reaction of the present invention, reaction pressure are normal pressure；Reaction temperature be 30~80 DEG C, preferably 40~ 60℃；Reaction time is 1~20h, preferably 6~18h.
Intermolecular hydrogen transfer reaction of the present invention is guard catalyst, reacts in inert gas such as nitrogen gas atmosphere Lower progress, oxygen volume content is in 10ppm or less.
In the present invention, after the reaction was completed, product dihydrocitronellal can be separated from system by way of rectifying.
Technical solution of the present invention has the active effect that
1) citral replaces hydrogenation method to obtain dihydrocitronellal by way of intermolecular hydrogen migration, avoids hydrogenation reaction High-temperature and high-pressure conditions, react milder compared with hydrogenation method, be easily manipulated, entire reaction carries out in nitrogen environment, improves Safety.
2) heterogeneous nickel catalyst is selected, catalyst is cheap to be easy to get, the intermolecular hydrogen of principal component efficient catalytic Transfer reaction realizes the selective hydrogenation to carbon-carbon double bond in hydrogen acceptor compound by addition Decanol iron cobalt, improves production The selectivity of object.
3) using alcohol compound as hydrogen donor, the dehydrogenation target by-product of high value is obtained.Due to dihydrocitronellal and hydrogen There are significant differences in terms of boiling point for target by-product after donor and its dehydrogenation, and dihydro lemongrass can be realized by way of rectifying The light separation of aldehyde, method is simple and easy, is suitable for actual production.
Detailed description of the invention
Fig. 1 is the infrared spectrum of Decanol iron cobalt.
Specific embodiment
The following examples will be further described technique provided by the present invention, but the present invention is not limited to listed Embodiment out should also include other any well known changes in interest field of the presently claimed invention.
One, primary raw material source in following embodiments and comparative example:
Citral: acid value 0.3mgKOH/g, BASF joint-stock company；
Anhydrous ferric chloride: Shanghai Aladdin biochemical technology limited liability company；
Waterless cobaltous chloride: Shanghai Aladdin biochemical technology limited liability company；
Decanol: Shanghai Aladdin biochemical technology limited liability company；
Heterogeneous nickel catalyst (nickel active carbon, nickel carbon nanotube, nickel aluminum oxide, nickel silica): nickle atom Load capacity 5wt%, Jiangsu Xinnuoke Catalyst Co., Ltd.；
Two, product analysis method is as follows in following embodiments and comparative example:
Gas chromatograph: Agilent7820A, gas chromatographic column: 30m × 0.25mm × 0.15 μm HP-INNOWAX column Temperature: 80 DEG C are kept for 2 minutes, are warming up to 2400 DEG C with 10 DEG C/min, are kept 10min；Injector temperature: 240 DEG C；Dottle pin purge gass Flow velocity: 3.0mL/min；Carrier gas (nitrogen) flow velocity: 1.0mL/min；Split sampling, split ratio 50:1；Detector: 260 DEG C；Hydrogen Flow: 30mL/min；Air mass flow: 400mL/min；Make-up gas flow: 25mL/min.
Infrared absorption spectrum analysis: the infrared transform spectrometer of Fourier produced using Perkinelmer Inc., the U.S. (FTIR) (model Spectrun One-B), analyzes bimetallic alkoxide.
The preparation method of Decanol iron cobalt
(1) molar ratio is that the iron chloride of 1:3 and Decanol are put into round-bottomed flask, and flask is placed in oil bath pan and is heated, It is reacted 8 hours at 250 DEG C, vacuum distillation obtains Decanol iron；
(2) molar ratio is that the cobalt chloride of 1:3 and Decanol are put into round-bottomed flask, and flask is placed in oil bath pan and is heated, It is reacted 8 hours at 250 DEG C, vacuum distillation obtains Decanol cobalt；
(3) molar ratio is that the Decanol iron of 1:1 and Decanol cobalt are put into round-bottomed flask, anti-at 280 DEG C using benzene as solvent 12 hours between seasonable, vacuum distillation obtains Decanol iron cobalt.
In the infrared spectrum of Fig. 1,576cm-1, 540.38cm-1, 468.84cm-1, it is the absorption peak of Decanol iron cobalt.
Citral acid value processing method
Citral (acid value 0.3mgKOH/g) removes heavy constituent, theoretical number of plates of rectifying tower using the mode of knifing rectifying 36 pieces, 120 DEG C of column bottom temperature, top vacuum degree 400Pa, reflux ratio 2:1, overhead extraction citral is surveyed using acid-base titration Citral acid value is 0.05mgKOH/g, the citral used as embodiment after fixed processing.