CN109651124A - The method for synthesizing p-tolyl aldehyde - Google Patents
The method for synthesizing p-tolyl aldehyde Download PDFInfo
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- CN109651124A CN109651124A CN201710934243.6A CN201710934243A CN109651124A CN 109651124 A CN109651124 A CN 109651124A CN 201710934243 A CN201710934243 A CN 201710934243A CN 109651124 A CN109651124 A CN 109651124A
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- tolyl aldehyde
- toluene
- catalyst
- ionic liquid
- method described
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- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 132
- -1 rare-earth salts Chemical class 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- 239000002608 ionic liquid Substances 0.000 claims abstract description 16
- 230000006315 carbonylation Effects 0.000 claims abstract description 8
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000006073 displacement reaction Methods 0.000 description 38
- 239000000203 mixture Substances 0.000 description 27
- 239000007789 gas Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- 238000009472 formulation Methods 0.000 description 12
- 229910052719 titanium Inorganic materials 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- 238000010792 warming Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- 229910017464 nitrogen compound Inorganic materials 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 235000011437 Amygdalus communis Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000220304 Prunus dulcis Species 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YNKMHABLMGIIFX-UHFFFAOYSA-N benzaldehyde;methane Chemical compound C.O=CC1=CC=CC=C1 YNKMHABLMGIIFX-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to the methods of synthesis p-tolyl aldehyde.Mainly solve the problems, such as that toluene conversion existing in the prior art and p-tolyl aldehyde yield are low, the present invention is by using the method for synthesizing p-tolyl aldehyde, it is included in catalyst Toluene and CO carries out carbonylation and obtains p-tolyl aldehyde, wherein the catalyst includes ionic liquid and rare-earth salts, the ionic liquid is selected from the ionic liquid with structural formula described in following formula, wherein R1And R2It is independently selected from C1~C4 alkyl, X is selected from PF6、SbF6、AlCl4、BF4、PF4、CF3COO、CF3SO3(CF3SO2)2The technical solution of at least one of N preferably resolves the technical problem, can be used in the industrial production of p-tolyl aldehyde.
Description
Technical field
The present invention relates to the methods of synthesis p-tolyl aldehyde.
Background technique
P-tolyl aldehyde is one of alkyl aromatic aldehyde, i.e. 4- tolyl aldehyde (p-Tolualdehyde, abbreviation
PTAL), it is colourless or light yellow transparent liquid, has the gentle fragrance of a flower and almond fragrance, there is certain stimulation to eyes and skin
Property.P-tolyl aldehyde can oxidative synthesis terephthalic acid (TPA) with high selectivity, while being also in a kind of important organic synthesis
Mesosome is widely used in fine chemistry industry and field of medicaments.
The synthetic method of p-tolyl aldehyde mainly has direct high-temperature oxidation, indirect electrosynthesis method and carbonylation method.
Direct high-temperature oxidation is to mix using paraxylene as raw material through light bromination, basic hydrolysis, hydrogen peroxide/hydrobromic acid
PTAL is made in liquid oxidation.Although the technique raw material is easy to get, is easy to operate, aromatic hydrocarbons utilization rate is low, technique is cumbersome, total conversion
Lower (26.7%) (Xiong Zhengchang, Jin Ningren, Hu Weixiao wait study on the synthesis [J] the Zhejiang Polytechnical University of p-tolyl aldehyde to learn
Report, 1999,27 (4)；334-337.).
Indirect electrosynthesis method is that catalysis oxidation paraxylene prepares PTAL in electrolytic cell, this method is simple, yield is higher,
Side reaction is few, blowdown is few, environmentally friendly and economize on resources, but since its used catalyst is expensive, the device is complicated, constrains it
Industrialization development (the work of the outer formula of Tang Duo, Wang Caihong, Li Yanwei slot ultrasonic indirect electrosynthesis benzaldehyde/p-tolyl aldehyde online
Skill improves [J] Institutes Of Technology Of Taiyuan journal, 2015,46 (1): 6-10.).
Carbonylation method is that toluene and CO catalysis of carbonyl are combined to PTAL.For the technique using CO as carbonylation agent, B-L is compound
One of liquid acid catalyst, solid super strong acids catalyst and ionic liquid class catalyst are catalyst, and reaction is real
Matter is that for CO to the electrophilic substitution reaction of toluene, referred to as Jia Teman-kock (Gattermann-Koch) synthesis is anti-under acid catalysis
It answers.This method atom utilization height, simple process, raw material CO are at low cost, have good market prospects.DuPont Corporation,
Mitsubishi gas company, Exxon Mobil company etc. have successively carried out research to the technique.With B-L composite fluid acid
Class, solid super strong acids catalyst are compared, the catalytic activity of the selective carbonylation of ionic liquid-catalyzed toluene and CO
It is obviously improved.Saleh is with [emim] Cl/AlCl3(xAlCl3It=0.75) is catalyst, the mass ratio of IL/ toluene is 8.5/
1.8, at room temperature, CO is kept to divide 8.2Mpa, reacts 1h, realize 66% toluene conversion and 89.1% PTAL selection rate
(Saleh RY,Rouge B.Process for making aromatic aldehydes using ionic liquids
[P].US:6320083,2001-11-20.).Its further application is the PTAL that will be isolated to through oxidative synthesis pair
Phthalic acid uses in the production of industrial polyester as monomer, and demand is larger.But in above-mentioned patent, there are catalyst
The problem that dosage is big, toluene conversion is low and p-tolyl aldehyde yield is low.
Summary of the invention
The technical problem to be solved by the present invention is to the low problems of toluene conversion and p-tolyl aldehyde yield, provide
A method of new synthesis p-tolyl aldehyde, this method have the spy of toluene conversion height and p-tolyl aldehyde high income
Point.
To solve the above-mentioned problems, The technical solution adopted by the invention is as follows:
The method for synthesizing p-tolyl aldehyde, is included in catalyst Toluene and CO carries out carbonylation acquisition pair
Tolyl aldehyde, wherein the catalyst includes ionic liquid and rare-earth salts, the ionic liquid, which is selected from, to be had described in following formula
The ionic liquid of structural formula:
Wherein R1And R2It is independently selected from C1~C4 alkyl, X is selected from PF6、SbF6、AlCl4、BF4、PF4、CF3COO、CF3SO3With
(CF3SO2)2At least one of N.
In above-mentioned technical proposal, the weight ratio of the catalyst and the toluene is preferably 1~12.
In above-mentioned technical proposal, the temperature of the reaction is preferably 20~150 DEG C.
In above-mentioned technical proposal, the pressure of the reaction is preferably 1~8MPa.
In above-mentioned technical proposal, the time of the reaction is preferably 1~12h.
In above-mentioned technical proposal, R1And R2Preferably different alkyl.Such as, but not limited to R1The R for methyl2Selected from ethyl
At least one of with butyl.
In above-mentioned technical proposal, X is selected from PF6And SbF6At least one of, it more preferably simultaneously include PF6And SbF6Two
Kind, which has synergistic effect in terms of improving toluene conversion.PF at this time6And SbF6Between ratio without spy
It does not limit, such as, but not limited to PF6And SbF6Molar ratio be 0.1~10, within this range more specifically infinite ratio be
0.2、0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5、2.0、2.5、3.0、3.5、4.0、4.5、
5.0,5.5,6.0,7.0,8.0,9.0 etc..
It can be 1- butyl -3- methylimidazole hexafluorophosphate, 1- positive third as ionic liquid described in non-restrictive
Base -3- methylimidazole hexafluorophosphate, 1- ethyl-3-methylimidazole hexafluorophosphate, N, N- methylimidazole hexafluorophosphate,
1- butyl -3- methylimidazole hexafluoro antimonate, 1- n-propyl -3- methylimidazole hexafluoro antimonate, 1- ethyl-3-methylimidazole six
Fluorine antimonate and N, one of N- methylimidazole hexafluoro antimonate.The more preferable ionic liquid is 1- butyl -3- methyl
At least one of imidazoles hexafluoro antimonate and 1- butyl -3- methylimidazole hexafluorophosphate.
In above-mentioned technical proposal, the rare-earth salts is preferably rare earth fluorinated alkyl sulfonate.
In above-mentioned technical proposal, the rare earth fluorinated alkyl sulfonate is preferably rare earth fluoroform sulphonate.
In above-mentioned technical proposal, the rare earth is preferably included selected from least one of scandium and cerium.
In above-mentioned technical proposal, the rare earth more preferably includes two kinds in scandium and cerium simultaneously, two kinds of rare earth elements
There is in terms of improving toluene conversion synergistic effect between fluorinated alkyl sulfonate.At this point, to the perfluor of two kinds of rare earth elements
Ratio is not particularly limited between alkylsulfonate, is such as, but not limited in mol 0.1~10, within this range more specifically
Infinite ratio be 0.2,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,2.0,2.5,
3.0,3.5,4.0,4.5,5.0,5.5,6.0,7.0,8.0,9.0 etc..
In above-mentioned technical proposal, the molar ratio of the ionic liquid and the rare-earth salts is preferably 1:(0.1~2).
In above-mentioned technical proposal, the catalyst preferably further includes promotor, the still more preferably described ionic liquid
The molar ratio of body, the rare-earth salts and the promotor is 1:(0.1~2): (0~0.5).
In above-mentioned technical proposal, the promotor is preferably at least one in heterocyclic nitrogen compound and organic phosphine compound
Kind.It include simultaneously more preferably heterocyclic nitrogen compound and organic phosphine compound, heterocyclic nitrogen compound and organic phosphine compound exist
There is synergistic effect in terms of improving p-tolyl aldehyde yield.At this point, ratio between two kinds of promotors is not particularly limited, example
Such as, but not limited to, the molar ratio of heterocyclic nitrogen compound and organic phosphine compound is 0.1~10, more specifically non-within this range
The ratio limited as 0.2,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,2.0,2.5,3.0,
3.5,4.0,4.5,5.0,5.5,6.0,7.0,8.0,9.0 etc..
In above-mentioned technical proposal, the heterocyclic nitrogen compound is in N-heterocyclic carbine, alkyl pyridine and Phen
At least one, further preferably Phen.
In above-mentioned technical proposal, the organic phosphine compound is preferably at least one in triphenylphosphine and tricyclohexyl phosphine
Kind.
In above-mentioned technical proposal, the preparation method of catalyst is not particularly limited, and can be mixed both according to required component
It can；Reaction system can also separately or concurrently be added according to required component in the reaction for synthesis of alkyl aromatic aldehyde, such as
If fruit is separately added into, the addition sequence of each component is also not particularly limited.
As non-restrictive, in the preparation of catalyst, when according to required component mixing, those skilled in the art
Member, which knows, preferably to carry out in CO atmosphere, to improve the solubility of CO；Rate is mixed in the catalyst components
100~800rpm；The catalyst components incorporation time is preferably 0.5h~2h.
The specific steps of synthesis p-tolyl aldehyde may is that
(1) catalyst components are added in autoclave；
(2) air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times, be stirred；
(3) alkylaromatic hydrocarbon is added, then with CO gas displacement 3 times；
(4) reaction pressure for being warming up to reaction temperature, keeping constant, stirring, is reacted, obtains alkyl aromatic containing product
The mixture of aldehyde.
In the present invention, if not specializing, pressure refers both to gauge pressure.
Sample treatment and analysis method are as follows:
With the ice water washed product mixture of 2 times of above-mentioned product mixtures volumes, water phase is discarded, by organic phase ether
Three times, the ether that extraction uses every time is equal with organic phase volume for extraction.Ether extraction liquid it will merge three times, revolving, residue
This crude product is carried out gas chromatographic analysis, calculates the conversion of toluene based on the analysis results by as p-tolyl aldehyde crude product
The yield of rate and p-tolyl aldehyde, calculation formula are as follows:
After technical solution of the present invention, for the conversion ratio of toluene up to 83.9%, the yield of p-tolyl aldehyde is reachable
76.8%, beneficial technical effect is achieved, can be used for toluene and CO carbonylation is prepared in the production of p-tolyl aldehyde.
Specific embodiment
[embodiment 1]
1- butyl -3- methylimidazole hexafluoro antimonate (0.5mol, 187g) and Sc are added in titanium autoclave
(CF3SO3)3(0.5mol, 246g), air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times；500rpm stirs 1h；Add
Enter toluene 110g；Air is with CO gas displacement 3 times in kettle；It is warming up to 50 DEG C, CO pressure 2.0MPa, 300rpm is kept to stir, instead
5h is answered, the product mixtures containing p-tolyl aldehyde are obtained.
For the ease of comparing and illustrate, catalyst formulation is listed in Table 1 below, the conversion ratio of toluene and p-tolyl aldehyde
Yield is listed in Table 2 below.
[embodiment 2]
1- butyl -3- methylimidazole hexafluorophosphate (0.5mol, 142g) and Sc are added in titanium autoclave
(CF3SO3)3(0.5mol, 246g), air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times；500rpm stirs 1h；Add
Enter toluene 110g；Air CO gas displacement in kettle；It is warming up to 50 DEG C, keeps CO pressure 2.0MPa, 300rpm stirring, reaction
5h obtains the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrate, catalyst formulation is listed in Table 1 below, the conversion ratio of toluene and p-tolyl aldehyde
Yield is listed in Table 2 below.
[embodiment 3]
1- butyl -3- methylimidazole hexafluoro antimonate (0.5mol, 187g) and Ce are added in titanium autoclave
(CF3SO3)3(0.5mol, 299g)；Air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times；500rpm stirs 1h；Add
Enter toluene 110g；Air is with CO gas displacement 3 times in kettle；It is warming up to 50 DEG C, CO pressure 2.0MPa, 300rpm is kept to stir, instead
5h is answered, the product mixtures containing p-tolyl aldehyde are obtained.
For the ease of comparing and illustrate, catalyst formulation is listed in Table 1 below, the conversion ratio of toluene and p-tolyl aldehyde
Yield is listed in Table 2 below.
[embodiment 4]
1- butyl -3- methylimidazole hexafluorophosphate (0.5mol, 142g) and Ce are added in titanium autoclave
(CF3SO3)3(0.5mol, 299g)；Air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times；500rpm stirs 1h；Add
Enter toluene 110g；Air is with CO gas displacement 3 times in kettle；It is warming up to 50 DEG C, CO pressure 2.0MPa, 300rpm is kept to stir, instead
5h is answered, the product mixtures containing p-tolyl aldehyde are obtained.
For the ease of comparing and illustrate, catalyst formulation is listed in Table 1 below, the conversion ratio of toluene and p-tolyl aldehyde
Yield is listed in Table 2 below.
[embodiment 5]
1- butyl -3- methylimidazole hexafluoro antimonate (0.25mol, 94g), 1- butyl-are added in titanium autoclave
3- methylimidazole hexafluorophosphate (0.25mol, 71g) and Sc (CF3SO3)3(0.5mol, 246g)；Air first uses N in kettle2Displacement
3 times, then with CO gas displacement 3 times；500rpm stirs 1h；Toluene 110g is added；Air is with CO gas displacement 3 times in kettle；Heating
To 50 DEG C, holding CO pressure 2.0MPa, 300rpm stirring, 5h is reacted, the product mixtures containing p-tolyl aldehyde are obtained.
For the ease of comparing and illustrate, catalyst formulation is listed in Table 1 below, the conversion ratio of toluene and p-tolyl aldehyde
Yield is listed in Table 2 below.
[embodiment 6]
1- butyl -3- methylimidazole hexafluoro antimonate (0.25mol, 94g), 1- butyl-are added in titanium autoclave
3- methylimidazole hexafluorophosphate (0.25mol, 71g) and Ce (CF3SO3)3(0.5mol, 299g)；Air first uses N in kettle2Displacement
3 times, then with CO gas displacement 3 times；500rpm stirs 1h；Toluene 110g is added；Air is with CO gas displacement 3 times in kettle；Heating
To 50 DEG C, holding CO pressure 2.0MPa, 300rpm stirring, 5h is reacted, the product mixtures containing p-tolyl aldehyde are obtained.
For the ease of comparing and illustrate, catalyst formulation is listed in Table 1 below, the conversion ratio of toluene and p-tolyl aldehyde
Yield is listed in Table 2 below.
[embodiment 7]
1- butyl -3- methylimidazole hexafluoro antimonate (0.5mol, 187g), Sc are added in titanium autoclave
(CF3SO3)3(0.25mol, 123g) and Ce (CF3SO3)3(0.25mol, 147g)；Air first uses N in kettle2Displacement 3 times, then use CO
Gas displacement 3 times；500rpm stirs 1h；Toluene 110g is added；Air is with CO gas displacement 3 times in kettle；It is warming up to 50 DEG C, keeps
CO pressure 2.0MPa, 300rpm stirring, reacts 5h, obtains the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrate, catalyst formulation is listed in Table 1 below, the conversion ratio of toluene and p-tolyl aldehyde
Yield is listed in Table 2 below.
[embodiment 8]
1- butyl -3- methylimidazole hexafluorophosphate (0.5mol, 142g), Sc are added in titanium autoclave
(CF3SO3)3(0.25mol, 123g) and Ce (CF3SO3)3(0.25mol, 147g)；Air first uses N in kettle2Displacement 3 times, then use CO
Gas displacement 3 times；500rpm stirs 1h；Toluene 110g is added；Air is with CO gas displacement 3 times in kettle；It is warming up to 50 DEG C, keeps
CO pressure 2.0MPa, 300rpm stirring, reacts 5h, obtains the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrate, catalyst formulation is listed in Table 1 below, the conversion ratio of toluene and p-tolyl aldehyde
Yield is listed in Table 2 below.
[embodiment 9]
1- butyl -3- methylimidazole hexafluoro antimonate (0.25mol, 94g), 1- butyl-are added in titanium autoclave
3- methylimidazole hexafluorophosphate (0.25mol, 71g), Sc (CF3SO3)3(0.25mol, 123g) and Ce (CF3SO3)3
(0.25mol, 147g)；Air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times；500rpm stirs 1h；Toluene is added
110g；Air is with CO gas displacement 3 times in kettle；It is warming up to 50 DEG C, keeps CO pressure 2.0MPa, 300rpm stirring is reacted 5h, obtained
Product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrate, catalyst formulation is listed in Table 1 below, the conversion ratio of toluene and p-tolyl aldehyde
Yield is listed in Table 2 below.
[embodiment 10]
1- butyl -3- methylimidazole hexafluoro antimonate (0.25mol, 94g), 1- butyl-are added in titanium autoclave
3- methylimidazole hexafluorophosphate (0.25mol, 71g), Sc (CF3SO3)3(0.25mol, 123g), Ce (CF3SO3)3
(0.25mol, 147g) and Phen (0.10mol, 19.8g)；Air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3
It is secondary；500rpm stirs 1h；Toluene 110g is added；Air is with CO gas displacement 3 times in kettle；It is warming up to 50 DEG C, keeps CO pressure
2.0MPa, 300rpm stirring, react 5h, obtain the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrate, catalyst formulation is listed in Table 1 below, the conversion ratio of toluene and p-tolyl aldehyde
Yield is listed in Table 2 below.
[embodiment 11]
1- butyl -3- methylimidazole hexafluoro antimonate (0.25mol, 94g), 1- butyl-are added in titanium autoclave
3- methylimidazole hexafluorophosphate (0.25mol, 71g), Sc (CF3SO3)3(0.25mol, 123g), Ce (CF3SO3)3
(0.25mol, 147g) and triphenylphosphine (0.10mol, 26g)；Air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3
It is secondary；500rpm stirs 1h；Toluene 110g is added；Air is with CO gas displacement 3 times in kettle；It is warming up to 50 DEG C, keeps CO pressure
2.0MPa, 300rpm stirring, react 5h, obtain the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrate, catalyst formulation is listed in Table 1 below, the conversion ratio of toluene and p-tolyl aldehyde
Yield is listed in Table 2 below.
[embodiment 12]
1- butyl -3- methylimidazole hexafluoro antimonate (0.25mol, 94g), 1- butyl-are added in titanium autoclave
3- methylimidazole hexafluorophosphate (0.25mol, 71g), Sc (CF3SO3)3(0.25mol, 123g), Ce (CF3SO3)3
(0.25mol, 147g), Phen (0.05mol, 10g) and triphenylphosphine (0.05mol, 13g)；Air first uses N in kettle2It sets
It changes 3 times, then with CO gas displacement 3 times；500rpm stirs 1h；Toluene 110g is added；Air is with CO gas displacement 3 times in kettle；It rises
Temperature reacts 5h, obtains the product mixtures containing p-tolyl aldehyde to 50 DEG C, holding CO pressure 2.0MPa, 300rpm stirring.
For the ease of comparing and illustrate, catalyst formulation is listed in Table 1 below, the conversion ratio of toluene and p-tolyl aldehyde
Yield is listed in Table 2 below.
Table 1
Table 2
| Conversion ratio/% of toluene | P-tolyl aldehyde yield/% | |
| Embodiment 1 | 68.6 | 51.9 |
| Embodiment 2 | 65.8 | 50.0 |
| Embodiment 3 | 64.0 | 46.7 |
| Embodiment 4 | 63.2 | 45.8 |
| Embodiment 5 | 71.5 | 52.3 |
| Embodiment 6 | 70.2 | 50.1 |
| Embodiment 7 | 73.0 | 61.8 |
| Embodiment 8 | 71.9 | 63.0 |
| Embodiment 9 | 80.5 | 62.4 |
| Embodiment 10 | 81.2 | 68.7 |
| Embodiment 11 | 81.7 | 71.0 |
| Embodiment 12 | 83.9 | 76.8 |
The above, the specific embodiment of part only of the present invention, but protection scope of the present invention is not limited to that,
Also any restrictions caused by not because of the precedence of each embodiment to the present invention, it is any to be familiar with person skilled in the art of the present invention
In the technical scope that the present invention reports, it can be changed or replace easily, should all cover within protection scope of the present invention.Cause
This, protection scope of the present invention is not limited only to above embodiments, it should be subject to the protection scope in claims.
Claims (8)
1. the method for synthesizing p-tolyl aldehyde, is included in catalyst Toluene and CO carries out carbonylation and obtains to first
Benzaldehyde, wherein the catalyst includes ionic liquid and rare-earth salts, the ionic liquid is selected to have and tie described in following formula
The ionic liquid of structure formula:
Wherein R1And R2It is independently selected from C1~C4 alkyl, X is selected from PF6、SbF6、AlCl4、BF4、PF4、CF3COO、CF3SO3With
(CF3SO2)2At least one of N.
2. according to the method described in claim 1, it is characterized in that the weight ratio of the catalyst and the toluene is 1~12.
3. according to the method described in claim 1, it is characterized in that the temperature of the reaction is 20~150 DEG C.
4. according to the method described in claim 1, it is characterized in that the pressure of the reaction is 1~8MPa.
5. according to the method described in claim 1, it is characterized in that the time of the reaction is 1~12h.
6. according to the method described in claim 1, it is characterized in that the rare-earth salts is rare earth fluorinated alkyl sulfonate.
7. according to the method described in claim 6, it is characterized in that the rare earth fluorinated alkyl sulfonate is rare earth trifluoromethanesulfonic acid
Salt.
8. according to the method described in claim 1, it is characterized in that the ionic liquid and the rare-earth salts molar ratio are 1:(0.1
~2).
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