CN113563165A - Preparation method of p-isopropylbenzaldehyde and p-isopropylbenzaldehyde synthesized from isopropylbenzene - Google Patents
Preparation method of p-isopropylbenzaldehyde and p-isopropylbenzaldehyde synthesized from isopropylbenzene Download PDFInfo
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- WTWBUQJHJGUZCY-UHFFFAOYSA-N cuminaldehyde Chemical compound CC(C)C1=CC=C(C=O)C=C1 WTWBUQJHJGUZCY-UHFFFAOYSA-N 0.000 title claims abstract description 111
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000012074 organic phase Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000012071 phase Substances 0.000 claims abstract description 48
- 230000007062 hydrolysis Effects 0.000 claims abstract description 45
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 claims abstract description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000007265 chloromethylation reaction Methods 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 15
- 238000005191 phase separation Methods 0.000 claims abstract description 13
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 11
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000012043 crude product Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 32
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 14
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 14
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims description 13
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 238000004886 process control Methods 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 54
- 238000000746 purification Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 27
- 238000007254 oxidation reaction Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 21
- 239000002994 raw material Substances 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 12
- 239000000543 intermediate Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 230000003472 neutralizing effect Effects 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 238000011208 chromatographic data Methods 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 5
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- CKMXAIVXVKGGFM-UHFFFAOYSA-N p-cumic acid Chemical compound CC(C)C1=CC=C(C(O)=O)C=C1 CKMXAIVXVKGGFM-UHFFFAOYSA-N 0.000 description 3
- CYAKWEQUWJAHLW-UHFFFAOYSA-N 1-(chloromethyl)-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(CCl)C=C1 CYAKWEQUWJAHLW-UHFFFAOYSA-N 0.000 description 2
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000005643 Gatterman-Koch carbonylation reaction Methods 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- -1 ammonium salt ions Chemical class 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QCJQHPTYZDBTEQ-UHFFFAOYSA-N C=1C=C(CCl)C=CC=1C(C)(C)C1=CC=CC=C1 Chemical compound C=1C=C(CCl)C=CC=1C(C)(C)C1=CC=CC=C1 QCJQHPTYZDBTEQ-UHFFFAOYSA-N 0.000 description 1
- 240000006927 Foeniculum vulgare Species 0.000 description 1
- 235000004204 Foeniculum vulgare Nutrition 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000006007 Sommelet synthesis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- XPQVQIJYDXCEKC-UHFFFAOYSA-K cerium(3+);methanesulfonate Chemical compound [Ce+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O XPQVQIJYDXCEKC-UHFFFAOYSA-K 0.000 description 1
- MQAKKMPOYHNCKJ-UHFFFAOYSA-N cerium;methane Chemical compound C.[Ce] MQAKKMPOYHNCKJ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
- C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/298—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with manganese derivatives
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Abstract
The invention provides a preparation method of p-isopropylbenzaldehyde and p-isopropylbenzaldehyde synthesized by isopropylbenzene, which comprises the following steps: chloromethylation, namely dripping hydrochloric acid into a solution of isopropyl benzene and aldehyde, heating to 80-88 ℃ after feeding, reacting, and separating phases to obtain an organic phase; step two, hydrolysis, namely mixing inorganic base, water and a phase transfer catalyst uniformly to prepare a hydrolysis solution, adding the organic phase obtained in the step one, heating to react under stirring, and then carrying out phase separation purification to obtain p-isopropyl benzyl alcohol; and step three, oxidizing, adding the p-isopropylbenzyl alcohol, the catalyst and the phase transfer catalyst obtained in the step two, heating, dropwise adding hydrogen peroxide for reaction, filtering, carrying out phase splitting on the filtrate to obtain a cuminaldehyde crude product, and purifying to obtain p-isopropylbenzaldehyde. The preparation method has the advantages of low cost, good process selectivity, mild process conditions and easy realization of industrialization.
Description
Technical Field
The invention relates to a preparation method of p-isopropylbenzaldehyde, in particular to a preparation method of p-isopropylbenzaldehyde synthesized by isopropylbenzene.
Background
P-isopropyl benzaldehyde, also known as cuminaldehyde, is used to prepare vegetable, spice, fennel and other fragrant edible essences. No mature industrial synthetic route is found for the synthesis of the p-isopropylbenzaldehyde at present, and the synthetic routes reported in the literature mainly comprise the following synthetic routes:
(1) p-cymene electrolytic oxidation method
P-cymene is used as a raw material, and is directly electrolyzed and oxidized to obtain p-isopropyl benzaldehyde and cuminic acid. The reaction process is as follows:
the use of Ce in the media electrochemical synthesis of aromatic aldehydes, ketones, and quinones using a cerium methane is reported by Kreh et al4+/Ce3+Redox couple, electrolysis of Ce in methanesulfonic acid medium (or directly using cerium methanesulfonate) from a diaphragm-containing plate-and-frame cell3+To Ce4+Then p-cymene is oxidized (40 ℃, 20min) in a reactor, the conversion rate is 20 percent, wherein the selectivity of p-methylacetophenone is 53 to 54 percent, and the selectivity of p-isopropylbenzaldehyde is 19 to 20 percent.
The method has short reaction time, but has harsh reaction conditions, more byproducts and great separation difficulty.
(2) Gatterman-Koch method
Yaoyongzheng et al "Fine chemical products Synthesis principle" reported that under Lewis acid and pressurization, the corresponding aromatic aldehyde can be generated under the action of the aromatic compound and the mixed gas of carbon monoxide and hydrogen chloride with equal amount of substances.
In the reaction, carbon monoxide reacts with hydrogen chloride to form an electrophilic intermediate [ HC+＝O]AlCl4 -The carbocation reacts with cumene to produce p-isopropyl benzaldehyde.
Cumene, however, is susceptible to disproportionation side reactions in the Gatterman-Koch reaction, resulting in low yields of p-isopropylbenzaldehyde.
(3) Trifluoroacetic acid process
In the organic intermediate preparation compiled by the State Master, Li reports that cumene is used as a raw material and reacts with trifluoroacetic acid and urotropine to obtain the product of p-isopropyl benzaldehyde. The reaction process is as follows:
the process of the method is lack of competitiveness because trifluoroacetic acid is expensive.
(4) Sommelet method
The method generally uses isopropyl benzene as a raw material, performs chloromethylation reaction, and then performs Sommelet reaction under an acidic condition to obtain a product of p-isopropyl benzaldehyde, wherein the reaction process is as follows:
the reaction firstly generates p-cumyl benzyl chloride, then ammonium salt ions are formed, the ammonium salt ions are hydrolyzed into benzylamine in acetic acid, the benzylamine is oxidized by azomethine released during hydrolysis, and then the p-isopropyl benzaldehyde is obtained through hydrolysis, but the yield is low.
(5) P-isopropyl benzoic acid process
Ziyong et al, in the literature, "synthetic research on p-isopropylbenzaldehyde", p-isopropylbenzoic acid is used as a raw material, and the product p-isopropylbenzaldehyde is obtained through three steps of esterification, reduction and oxidation, wherein DMF is used as a catalyst in the esterification reaction, other reagents comprise methanol and thionyl chloride, and the esterification yield is 89.8%; the reduction process adopts tetrahydrofuran as a solvent and sodium borohydride as a reducing agent, and the yield is 92%; the oxidation process adopts dichloromethane as a solvent and a mixture of potassium permanganate and copper sulfate as an oxidant, and the reaction is carried out at normal temperature, wherein the yield is 89.3%; the reported product purity was 98.6% with an overall yield of 73.8%. The reaction process is as follows:
the process uses a large amount of flammable and explosive solvents such as thionyl chloride, dichloromethane and the like, uses a large amount of reducing agents and oxidizing agents such as sodium borohydride, potassium permanganate and the like, does not meet the requirements of environmental protection at present, and has poor process safety and incapability of realizing large-scale industrial production.
At present, a new process which is low in cost, good in process selectivity, mild in process conditions and easy to realize industrialization does not exist.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of p-isopropylbenzaldehyde and p-isopropylbenzaldehyde synthesized by isopropylbenzene, which has the advantages of low cost, good process selectivity, mild process conditions and easy realization of industrialization, and is a safe and environment-friendly new process.
In order to attain the above and other related objects,
the invention provides a preparation method of p-isopropyl benzaldehyde and p-isopropyl benzaldehyde synthesized by isopropyl benzene, which comprises the following steps:
step one, chloromethylation, adding 600 parts by weight of cumene and 0.2-0.3 part by weight of aldehyde solution into a reaction kettle, heating to 40-120 ℃, then dropwise adding 2500 parts by weight of hydrochloric acid into the reaction kettle, heating to 80-88 ℃ after the addition of the hydrochloric acid, keeping the temperature for reaction for 1-6h, standing and phase splitting to obtain an organic phase;
step two, hydrolysis, namely adding 120 parts by weight of inorganic base 100, 7180 parts by weight of water 7000, and 7180 parts by weight of phase transfer catalyst 27.5-34.5 parts by weight into a reaction kettle, uniformly mixing to prepare a hydrolysis solution, then adding the organic phase obtained in the step one, heating to 80-105 ℃ under stirring, reacting for 6-16h, standing for phase splitting, washing the organic phase, removing the solvent, and purifying to obtain p-isopropyl benzyl alcohol;
and step three, oxidizing, namely adding the p-isopropylbenzyl alcohol obtained in the step two, 1.8-2.5 parts by weight of catalyst and 0.9-1.25 parts by weight of phase transfer catalyst into a reaction kettle, heating in a water bath to 45-100 ℃, dropwise adding 150 parts by weight of hydrogen peroxide, keeping the temperature of a dropwise adding process control system unchanged, continuing to react for 2-8 hours after dropwise adding is finished, filtering, carrying out phase separation on filtrate, washing an organic phase to obtain a crude product of cuminaldehyde, and purifying the crude product of cuminaldehyde to obtain p-isopropylbenzaldehyde.
By adopting the technical scheme, the cumene is used as a production raw material, so that the cost is low; the whole process has good selectivity, wherein the content of chloromethylation raw material addition product (ortho-meta-pair) is more than 99 percent, the content of hydrolysis process raw material addition product is more than 95 percent, and the content of oxidation process product addition product is more than 95 percent; the process conditions are mild, wherein the temperature of the chloromethylation reaction is 40-120 ℃, the temperature of the hydrolysis process reaction is 80-105 ℃, and the temperature of the oxidation process reaction is 45-100 ℃, so that the process is easy to realize industrialization and is a safe and environment-friendly new process.
The chloromethylation adopts high-concentration hydrochloric acid, cumene, aldehyde solution and the like as main raw materials, and performs chloromethylation reaction at a certain temperature to generate an intermediate, the selectivity of monochloromethylation of the cumene is good, and the excess cumene can be recycled by simple distillation.
The hydrolysis process adopts alkaline aqueous solution and p-isopropyl benzyl chloride for reaction, the conversion rate of an intermediate is more than 99 percent, and the selectivity is good.
The oxidation process adopts hydrogen peroxide as an oxidant to react under the action of a catalyst, the process conditions are mild, the conversion rate of an intermediate is more than 92%, and the selectivity is more than 95%.
In an embodiment of the present invention, in the first step, the aldehyde solution is paraformaldehyde.
Through the technical scheme, the test process finds that at least one of paraformaldehyde, formaldehyde or trioxymethylene can obtain good effect as the aldehyde solution in the first step, and the chloromethylation reaction of the paraformaldehyde is carried out to generate an intermediate, so that the selectivity of the monochloro methylation of the isopropylbenzene is better.
In an embodiment of the present invention, the inorganic base in the second step is sodium carbonate.
Through the technical scheme, the experiment process finds that at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide and sodium hydrogen phosphate has good effect as the inorganic base in the second step, but the sodium carbonate is relatively low in price and more suitable for industrialization, and the sodium carbonate as the inorganic base has higher reaction speed with p-isopropyl benzyl chloride, better selectivity and fewer side reactions, so that the product yield can be further improved.
In one embodiment of the present invention, the phase transfer catalyst in step two and step three is tetrabutylammonium bromide.
Through the technical scheme, in the experimental process, at least one of tetrabutylammonium bromide, hexadecyltrimethylammonium bromide, tetrabutylammonium chloride, methyl triphenyl phosphonium bromide and tetraphenyl phosphonium bromide is used as a phase transfer catalyst, so that a reactant can be transferred from one phase to another phase capable of reacting, the reaction rate of an out-of-phase system is accelerated, when tetrabutylammonium bromide is selected, the price is cheaper, the reaction rate is faster, the yield of an intermediate product obtained in the same time is higher, and the method is more suitable for industrialization.
In an embodiment of the present invention, in step three, the catalyst is tungsten trioxide.
By adopting the technical scheme, vanadium pentoxide, titanium oxide, palladium acetate, palladium chloride, ferric nitrate, cobalt hydroxide, cerium oxide and Au/Al2O3At least one of phosphotungstic acid, tungstic acid, sodium tungstate and tungsten trioxide is used as the catalyst in the third step, the reaction rate can be accelerated, but different catalyst process conditions, such as temperature, time and the like, have different effects, and can generate higher yield, wherein the yield of the tungsten trioxide used as the catalyst is highest. In addition, the price of the catalyst is greatly different, the cost of the tungsten trioxide is lower, and the method is more suitable for industrialization.
In a second aspect of the present invention, there is provided p-isopropylbenzaldehyde obtainable by any one of the above-mentioned processes.
As mentioned above, the preparation method of the p-isopropyl benzaldehyde and the p-isopropyl benzaldehyde synthesized by isopropyl benzene has the following beneficial effects:
1. solves the technological problem of synthesizing p-isopropyl benzaldehyde from isopropyl benzene, and obtains the product p-isopropyl benzaldehyde through three steps of chloromethylation, hydrolysis and oxidation. The process has low cost of raw materials; the process selectivity is good, wherein the content of chloromethylation raw material addition product (ortho-meta pair) is more than 99%, the content of hydrolysis process raw material addition product is more than 95%, and the content of oxidation process product addition product is more than 95%; the process conditions are mild, wherein the temperature of the chloromethylation reaction is 40-120 ℃, the temperature of the hydrolysis process reaction is 80-105 ℃, the temperature of the oxidation process reaction is 45-100 ℃, the industrialization is easy to realize, and the method is a safe and environment-friendly new process.
Drawings
FIG. 1 is a flow chart of a method provided herein;
FIG. 2 is a chromatogram of the chloromethylation reaction intermediate of example 5 of the present application;
FIGS. 3 and 4 are the results of the analysis of FIG. 2;
FIG. 5 is a chromatogram of an intermediate product of a hydrolysis reaction in example 5 of the present application;
FIGS. 6 and 7 are the results of the analysis of FIG. 5;
FIG. 8 is a chromatogram of an oxidation reaction intermediate of example 5 of the present application;
FIGS. 9 and 10 are the results of the analysis of FIG. 8;
FIG. 11 is a chromatogram of the product of example 5 of the present application;
fig. 12 is the analysis result of fig. 11.
Detailed Description
Other advantages and capabilities of the present invention will be readily apparent to those skilled in the art from the disclosure of the present specification by describing the embodiments of the present invention with reference to the specific embodiments thereof.
The starting materials of the present invention are all commercially available.
Example 1
A preparation method for synthesizing p-isopropylbenzaldehyde from cumene comprises the following steps:
step one, chloromethylation reaction
Adding 500kg of isopropyl benzene and 200g of formaldehyde into a 5000L reaction kettle, heating to 40 ℃, then beginning to dropwise add 36.5% hydrochloric acid, dropwise adding 2500kg within 1h, continuing to heat to 80 ℃ after the addition of the system temperature is finished, maintaining the temperature for reaction for 1h, standing for phase separation after the reaction is finished, and obtaining an organic phase and an inorganic phase, wherein the inorganic phase is waste acid and can be recycled;
step two, hydrolysis reaction
Adding 100kg of sodium hydroxide, 7000kg of pure water and 27.5kg of hexadecyl trimethyl ammonium bromide into a 10000L reaction kettle, uniformly mixing to prepare a hydrolysis solution, then adding the organic phase obtained in the step one, heating to 80 ℃ under stirring, then reacting for 6 hours, after the reaction is finished, standing for phase splitting, washing the organic phase once by using 250kg of clear water to obtain a hydrolysis organic phase, neutralizing the water phase to be neutral by using 36.5% hydrochloric acid, then returning for recycling, only adding inorganic base for subsequent hydrolysis, washing the hydrolysis organic phase once by using clear water, then putting the hydrolysis organic phase into a 1000L distillation kettle to distill and remove a solvent cumene, returning the removed cumene solvent to chloromethylation for direct use, cooling the organic phase, and then rectifying to obtain high-content p-isopropyl benzyl alcohol;
step three, oxidation reaction
Adding the p-isopropyl benzyl alcohol, vanadium pentoxide and tetrabutyl ammonium chloride obtained in the second step into a 500L reaction kettle, heating the mixture in a water bath to 45 ℃, dropwise adding 115kg of hydrogen peroxide within 1h, controlling the temperature of the system to be constant at 45 ℃ in the dropwise adding process, continuing to react for 2h after the dropwise adding is finished, pouring out the materials after the reaction is finished, filtering, directly returning the filtered catalyst for continuous use, carrying out phase splitting on the filtrate, treating the water phase in wastewater, washing the organic phase once by using 50kg of 10% sodium carbonate solution, washing once by using 100g of clear water to obtain an oxidized organic phase, adding the oxidized organic phase into a 500L rectifying kettle, controlling the vacuum degree of the system to be 500pa, and controlling the temperature of the rectifying kettle to be 110 ℃ to obtain cuminaldehyde.
Example 2
Step one, chloromethylation reaction
Adding 500kg of isopropyl benzene and 200g of paraformaldehyde into a 5000L reaction kettle, heating to above 40 ℃, then starting to dropwise add 36.5% hydrochloric acid, dropwise adding 2500kg within 1h, keeping the temperature to 80 ℃ after the addition is finished, keeping the temperature for reaction for 1h, standing for phase separation after the reaction is finished, obtaining an organic phase and an inorganic phase, wherein the inorganic phase is waste acid and can be recycled;
adding 100kg of sodium hydroxide, 7000kg of pure water and 27.5kg of hexadecyl trimethyl ammonium bromide into a 10000L reaction kettle, uniformly mixing to prepare a hydrolysis solution, then adding the organic phase obtained in the step one, heating to 80 ℃ under stirring, then reacting for 6 hours, after the reaction is finished, standing for phase splitting, washing the organic phase once by using 250kg of clear water to obtain a hydrolysis organic phase, neutralizing the water phase to be neutral by using 36.5% hydrochloric acid, then returning for recycling, only adding inorganic base for subsequent hydrolysis, washing the hydrolysis organic phase once by using clear water, then putting the hydrolysis organic phase into a 1000L distillation kettle to distill and remove a solvent cumene, returning the removed cumene solvent to chloromethylation for direct use, cooling the organic phase, and then rectifying to obtain high-content p-isopropyl benzyl alcohol;
step three, oxidation reaction
Adding the p-isopropyl benzyl alcohol, vanadium pentoxide and tetrabutyl ammonium chloride obtained in the second step into a 500L reaction kettle, heating the mixture in a water bath to 45 ℃, dropwise adding 115kg of hydrogen peroxide within 1h, controlling the temperature of the system to be constant at 45 ℃ in the dropwise adding process, continuing to react for 2h after the dropwise adding is finished, pouring out the materials after the reaction is finished, filtering, directly returning the filtered catalyst for continuous use, carrying out phase splitting on the filtrate, treating the water phase in wastewater, washing the organic phase once by using 50kg of 10% sodium carbonate solution, washing once by using 100g of clear water to obtain an oxidized organic phase, adding the oxidized organic phase into a 500L rectifying kettle, controlling the vacuum degree of the system to be 500pa, and controlling the temperature of the rectifying kettle to be 110 ℃ to obtain cuminaldehyde.
Example 3
Step one, chloromethylation reaction
Adding 500kg of isopropyl benzene and 200g of paraformaldehyde into a 5000L reaction kettle, heating to 40 ℃, then starting to dropwise add 36.5% hydrochloric acid, dropwise adding 2500kg within 1h, keeping the temperature to 80 ℃ after the addition is finished, continuously heating to 80 ℃, maintaining the temperature for reaction for 1h, standing for phase separation after the reaction is finished, and obtaining an organic phase and an inorganic phase, wherein the inorganic phase is waste acid and can be recycled;
step two, hydrolysis reaction
Adding 100kg of sodium carbonate, 7000kg of pure water and 27.5kg of hexadecyl trimethyl ammonium bromide into a 10000L reaction kettle, uniformly mixing to prepare a hydrolysis solution, then adding the organic phase obtained in the step one, heating to 80 ℃ under stirring, then reacting for 6h, after the reaction is finished, standing for phase splitting, washing the organic phase once by using 250kg of clear water to obtain a hydrolysis organic phase, neutralizing the water phase to be neutral by using 36.5% hydrochloric acid, then returning for recycling, only adding inorganic base for subsequent hydrolysis, washing the hydrolysis organic phase once by using the clear water, then putting the hydrolysis organic phase into a 1000L distillation kettle for distillation to remove a solvent cumene, returning the removed cumene solvent to chloromethylation for direct use, cooling the organic phase, and then rectifying to obtain high-content p-isopropyl benzyl alcohol;
step three, oxidation reaction
Adding the p-isopropyl benzyl alcohol, vanadium pentoxide and tetrabutyl ammonium chloride obtained in the second step into a 500L reaction kettle, heating the mixture in a water bath to 45 ℃, dropwise adding 115kg of hydrogen peroxide within 1h, controlling the temperature of the system to be constant at 45 ℃ in the dropwise adding process, continuing to react for 2h after the dropwise adding is finished, pouring out the materials after the reaction is finished, filtering, directly returning the filtered catalyst for continuous use, carrying out phase splitting on the filtrate, treating the water phase in wastewater, washing the organic phase once by using 50kg of 10% sodium carbonate solution, washing once by using 100g of clear water to obtain an oxidized organic phase, adding the oxidized organic phase into a 500L rectifying kettle, controlling the vacuum degree of the system to be 500pa, and controlling the temperature of the rectifying kettle to be 113 ℃ to obtain cuminaldehyde.
Example 4
Step one, chloromethylation reaction
Adding 500kg of isopropyl benzene and 200g of paraformaldehyde into a 5000L reaction kettle, heating to 40 ℃, then starting to dropwise add 36.5% hydrochloric acid, dropwise adding 2500kg within 1h, keeping the temperature to 80 ℃ after the addition is finished, continuously heating to 80 ℃, maintaining the temperature for reaction for 1h, standing for phase separation after the reaction is finished, and obtaining an organic phase and an inorganic phase, wherein the inorganic phase is waste acid and can be recycled;
step two, hydrolysis reaction
Adding 100kg of sodium carbonate, 7000kg of pure water and 27.5kg of tetrabutylammonium bromide into a 10000L reaction kettle, uniformly mixing to prepare a hydrolysis solution, then adding the organic phase obtained in the step one, heating to 80 ℃ under stirring, then reacting for 6 hours, after the reaction is finished, standing for phase splitting, washing the organic phase once by using 250kg of clear water to obtain a hydrolysis organic phase, neutralizing the water phase to be neutral by using 36.5% hydrochloric acid, then returning to reuse, only adding inorganic base for subsequent hydrolysis, washing the hydrolysis organic phase once by using clear water, then putting the hydrolysis organic phase into a 1000L distillation kettle to distill and remove a solvent cumene, returning the removed cumene solvent to chloromethylation for direct use, cooling the organic phase, and then rectifying to obtain high-content p-isopropylbenzyl alcohol;
step three, oxidation reaction
Adding the p-isopropyl benzyl alcohol, vanadium pentoxide and tetrabutyl ammonium chloride obtained in the second step into a 500L reaction kettle, heating the mixture in a water bath to 45 ℃, dropwise adding 115kg of hydrogen peroxide within 1h, controlling the temperature of the system to be constant at 45 ℃ in the dropwise adding process, continuing to react for 2h after the dropwise adding is finished, pouring out the materials after the reaction is finished, filtering, directly returning the filtered catalyst for continuous use, carrying out phase splitting on the filtrate, treating the water phase in wastewater, washing the organic phase once by using 50kg of 10% sodium carbonate solution, washing once by using 100g of clear water to obtain an oxidized organic phase, adding the oxidized organic phase into a 500L rectifying kettle, controlling the vacuum degree of the system to be 500pa, and controlling the temperature of the rectifying kettle to be 110 ℃ to obtain cuminaldehyde.
Example 5
Step one, chloromethylation reaction
Adding 500kg of isopropyl benzene and 200g of paraformaldehyde into a 5000L reaction kettle, heating to 60 ℃, then starting to dropwise add 36.5% hydrochloric acid, dropwise adding 2500kg within 1h, keeping the temperature to 80 ℃ after the addition is finished, continuously heating to 80 ℃, maintaining the temperature for reaction for 1h, standing for phase separation after the reaction is finished, and obtaining an organic phase and an inorganic phase, wherein the inorganic phase is waste acid and can be recycled;
step two, hydrolysis reaction
Adding 100kg of sodium carbonate, 7000kg of pure water and 27.5kg of tetrabutylammonium bromide into a 10000L reaction kettle, uniformly mixing to prepare a hydrolysis solution, then adding the organic phase obtained in the step one, heating to reflux under stirring, then reacting for 6h, standing for phase splitting after the reaction is finished, washing the organic phase once by using 250kg of clear water to obtain a hydrolysis organic phase, neutralizing the water phase to be neutral by using 36.5% hydrochloric acid, then returning to reuse, only adding inorganic base for subsequent hydrolysis, washing the hydrolysis organic phase once by using clear water, then putting the hydrolysis organic phase into a 1000L distillation kettle to distill and remove a solvent cumene, returning the removed cumene solvent to chloromethylation for direct use, cooling the organic phase, and then rectifying to obtain high-content p-isopropylbenzyl alcohol;
step three, oxidation reaction
Adding the p-isopropyl benzyl alcohol, 1.8kg of tungsten trioxide and 0.9kg of tetrabutylammonium bromide obtained in the second step into a 500L reaction kettle, heating the mixture in a water bath to 66 ℃, dropwise adding 115kg of hydrogen peroxide within 1 hour, controlling the temperature of a system to be unchanged in the dropwise adding process, continuing to react for 2 hours after the dropwise adding is finished, pouring out the materials after the reaction is finished, filtering, directly returning the filtered catalyst for continuous use, carrying out phase separation on the filtrate, treating the water phase in wastewater, washing the organic phase once by using 50kg of 10% sodium carbonate solution, washing once by using 100g of clear water to obtain an oxidized organic phase, adding the oxidized organic phase into a 500L rectifying kettle, controlling the vacuum degree of the system to be 500pa, and controlling the temperature of the rectifying kettle to be 110 ℃ to obtain cuminaldehyde.
Example 6
Step one, chloromethylation reaction
Adding 550kg of isopropyl benzene and 250g of paraformaldehyde into a 5000L reaction kettle, heating to 80 ℃, then beginning to dropwise add 36.5% hydrochloric acid, dropwise adding 2600kg within 1h, continuing to heat to 83 ℃ after the addition of the system temperature is 70-72 ℃, keeping the temperature for reaction for 1.3h, standing for phase separation after the reaction is finished, and obtaining an organic phase and an inorganic phase, wherein the inorganic phase is waste acid and can be recycled;
step two, hydrolysis reaction
Adding 110kg of sodium carbonate, 7100kg of pure water and 30.5kg of tetrabutylammonium bromide into a 10000L reaction kettle, uniformly mixing to prepare a hydrolyzed solution, then adding the organic phase obtained in the step one, heating to 95 ℃ under stirring, reacting for about 10 hours, standing for phase splitting after the reaction is finished, washing the organic phase once by using 250kg of clear water to obtain a hydrolyzed organic phase, neutralizing the water phase to be neutral by using 36.5% hydrochloric acid, then returning for recycling, only adding inorganic base for subsequent hydrolysis, washing the hydrolyzed organic phase once by using clear water, then putting the hydrolyzed organic phase into a 1000L distillation kettle to distill and remove a solvent cumene, returning the removed cumene solvent to chloromethylation for direct use, cooling the organic phase, and then rectifying to obtain high-content p-isopropylbenzyl alcohol;
step three, oxidation reaction
Adding the p-isopropyl benzyl alcohol, tungsten trioxide and tetrabutylammonium bromide obtained in the second step into a 500L reaction kettle, heating the mixture in a water bath to 66 ℃, dropwise adding 130kg of hydrogen peroxide within 1.3h, controlling the temperature of the system in the dropwise adding process to be unchanged at 66 ℃, continuing to react for 6h after the dropwise adding is finished, pouring out the materials after the reaction is finished, filtering, directly returning the filtered catalyst for continuous use, carrying out phase separation on the filtrate, treating the water phase in wastewater, washing the organic phase once by using a 10% sodium carbonate solution of 50kg, washing once by using 100g of clear water to obtain an oxidized organic phase, adding the oxidized organic phase into a 500L rectifying kettle, controlling the vacuum degree of the system to be 500pa, and controlling the temperature of the rectifying kettle to be 113 ℃ to obtain cuminic aldehyde.
Example 7
Step one, chloromethylation reaction
Adding 600kg of isopropyl benzene and 300g of paraformaldehyde into a 5000L reaction kettle, heating to 120 ℃, then beginning to dropwise add 36.5% hydrochloric acid, dropwise adding 2700kg within 1.5h, keeping the temperature at 70-72 ℃ after the addition, continuously heating to 88 ℃, maintaining the temperature for reaction for 6h, standing for phase separation after the reaction is finished, and obtaining an organic phase and an inorganic phase, wherein the inorganic phase is waste acid and can be recycled;
step two, hydrolysis reaction
Adding 120kg of sodium carbonate, 7180kg of pure water and 34.5kg of tetrabutylammonium bromide into a 10000L reaction kettle, uniformly mixing to prepare a hydrolyzed solution, then adding the organic phase obtained in the step one, heating to 105 ℃ under stirring, reacting for about 6 hours, standing for phase splitting after the reaction is finished, washing the organic phase once by using 300kg of clear water to obtain a hydrolyzed organic phase, neutralizing the water phase to be neutral by using 36.5% hydrochloric acid, then returning for recycling, only adding inorganic base for subsequent hydrolysis, washing the hydrolyzed organic phase once by using clear water, then putting the hydrolyzed organic phase into a 1000L distillation kettle to distill and remove a solvent cumene, returning the removed cumene solvent to chloromethylation for direct use, cooling the organic phase, and then rectifying to obtain high-content p-isopropylbenzyl alcohol;
step three, oxidation reaction
Adding the p-isopropyl benzyl alcohol, 2.5kg of tungsten trioxide and 1.25kg of tetrabutylammonium bromide obtained in the second step into a 500L reaction kettle, heating the mixture in a water bath to 100 ℃, dropwise adding 150kg of hydrogen peroxide within 1.5h, controlling the temperature of the system to be 100 ℃ in the dropwise adding process to be unchanged, continuing to react for 8h after the dropwise adding is finished, pouring out the materials after the reaction is finished, filtering, directly returning the filtered catalyst for continuous use, carrying out phase separation on the filtrate, treating the water phase in wastewater, washing the organic phase once by using 60kg of 10% sodium carbonate solution, washing once by using 100g of clear water to obtain an oxidized organic phase, adding the oxidized organic phase into a 500L rectifying kettle, controlling the vacuum degree of the system to be 500pa, and controlling the temperature of the rectifying kettle to be 115 ℃ to obtain cuminaldehyde.
Test result detection method
1. Product or intermediate detection: the intermediates and products of the chloromethylation, hydrolysis and oxidation reactions were quantitatively and qualitatively analyzed by a gas chromatograph model GC9790II, wherein the parameters of the gas chromatograph were as follows: a chromatographic column: SE-54, 50 m capillary column, film thickness 0.25 μm, inner diameter 0.32 mm; stationary phase: 95% methylpolysiloxane, 5% phenyl; carrier gas: n is a radical of2(ii) a Sample introduction amount: 0.1 μ l; column temperature: 100 ℃ to 230 ℃; a detector: FID; detector temperature: 250 ℃; sample inlet temperature: 230 ℃ to 230 ℃.
Examples 1-7 chloromethylation reactions the chromatographic data are shown in Table 1
TABLE 1 chromatographic data for chloromethylation reactions of examples 1-7
Examples 1-7 chromatographic data for hydrolysis reactions are shown in Table 2
TABLE 2 chromatographic data for hydrolysis reactions of examples 1-7
Chromatographic data for oxidation reactions of examples 1-7 are shown in Table 3
TABLE 3 chromatographic data for oxidation reactions of examples 1-7
Analysis of results
As can be seen by combining examples 1-7 and tables 1-3, the process problem of synthesizing the p-isopropyl benzaldehyde from the isopropylbenzene is solved by the three-step synthesis process of chloromethylation, hydrolysis and oxidation, and the process raw material cost is low; the process selectivity is good, wherein the content of the chloromethylation raw material addition product (ortho-meta pair) is more than 90 percent, and the content of the oxidation process product is more than 94 percent; the process conditions are mild, wherein the temperature of the chloromethylation reaction is 40-120 ℃, the temperature of the hydrolysis process reaction is 80-105 ℃, the temperature of the oxidation process reaction is 45-100 ℃, the industrialization is easy to realize, and the method is a safe and environment-friendly new process.
As can be seen by combining examples 1-2 with tables 1-3, when example 2 was performed in step one by chloromethylation using paraformaldehyde instead of formaldehyde as the aldehyde solution in example 1, the yield of intermediates in the organic phase was greater and the content of chloromethylated starting material plus product (ortho-para) increased, and it can be seen that chloromethylation using paraformaldehyde instead of formaldehyde as the aldehyde solution resulted in better selectivity for cumene monochloromethylation. Further, the yield of the intermediate product in the second step is increased, and the yield of the product in the third step is increased.
As can be seen by combining examples 2-3 with tables 1-3, when sodium carbonate is used in example 3 instead of sodium hydroxide as the inorganic base in example 2, the yield of the intermediate product in step one and the content of the chloromethylation raw material and the product (o-m pair) in example 3 are not much different from those in example 2, but the yield of the intermediate product hydrolysis organic phase in step two is increased, and the yield of the product in step three is also increased.
As can be seen by combining examples 3-4 with tables 1-3, tetrabutylammonium bromide was used as the phase transfer catalyst in example 4 instead of cetyltrimethylammonium bromide in example 3, and the yields of the intermediate product in step two and the product in step three in example 4 were all higher than in example 3, which shows that tetrabutylammonium bromide catalyzed the reaction faster and the product obtained in the same time was more productive.
As can be seen by combining examples 4-5 with tables 1-3, example 5 employs tungsten trioxide in place of the vanadium pentoxide of example 4 as the catalyst, and as a result, the product yield in step three of example 5 is greater than that of example 4, and it can be seen that the yield of tungsten trioxide as the catalyst is higher.
Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method for synthesizing p-isopropylbenzaldehyde from isopropylbenzene is characterized by comprising the following steps:
chloromethylation, adding 500-2700 parts of cumene and 0.2-0.3 part of aldehyde solution by weight, heating to 40-120 ℃, then adding 2500-2700 parts of hydrochloric acid by weight, heating to 80-88 ℃ after finishing adding, keeping the temperature for reaction for 1-6h, standing and phase splitting to obtain an organic phase;
step two, hydrolysis, namely uniformly mixing 120 parts by weight of inorganic base 100, 7180 parts by weight of water 7000, and 7180 parts by weight of phase transfer catalyst 27.5-34.5 parts by weight to prepare a hydrolysis solution, then adding the organic phase obtained in the step one, heating to 80-105 ℃ under stirring, reacting for 6-16h, standing for phase splitting, washing the organic phase, removing the solvent, and purifying to obtain p-isopropyl benzyl alcohol;
and step three, oxidizing, namely adding the p-isopropyl benzyl alcohol obtained in the step two, 1.8-2.5 parts by weight of catalyst and 0.9-1.25 parts by weight of phase transfer catalyst, heating in a water bath to 45-100 ℃, dropwise adding 150 parts by weight of hydrogen peroxide, keeping the temperature of a dropwise adding process control system unchanged, continuing to react for 2-8 hours after dropwise adding is finished, filtering, carrying out phase separation on filtrate, washing an organic phase to obtain a crude product of cuminaldehyde, and purifying the crude product of cuminaldehyde to obtain the p-isopropyl benzaldehyde.
2. The method for preparing p-isopropylbenzaldehyde from cumene according to claim 1, wherein the method comprises the following steps: the aldehyde solution in step one comprises at least one of paraformaldehyde, formaldehyde or trioxymethylene.
3. The method for preparing p-isopropylbenzaldehyde from cumene according to claim 1, wherein the method comprises the following steps: in the step one, the aldehyde solution is paraformaldehyde.
4. The method for preparing p-isopropylbenzaldehyde from cumene according to claim 1, wherein the method comprises the following steps: and in the second step, the inorganic base comprises at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide and sodium hydrogen phosphate.
5. The method for preparing p-isopropylbenzaldehyde from cumene according to claim 1, wherein the method comprises the following steps: and in the second step, the inorganic alkali is sodium carbonate.
6. The method for preparing p-isopropylbenzaldehyde from cumene according to claim 1, wherein the method comprises the following steps: the phase transfer catalyst in the second step and the third step comprises at least one of tetrabutylammonium bromide, hexadecyltrimethylammonium bromide, tetrabutylammonium chloride, methyl triphenyl phosphonium bromide and tetraphenyl phosphonium bromide.
7. The method for preparing p-isopropylbenzaldehyde from cumene according to claim 1, wherein the method comprises the following steps: in the second step and the third step, the phase transfer catalyst is tetrabutylammonium bromide.
8. The method for preparing p-isopropylbenzaldehyde from cumene according to claim 1, wherein the method comprises the following steps: the catalyst in the third step comprises vanadium pentoxide, titanium oxide, palladium acetate, palladium chloride, ferric nitrate, cobalt hydroxide, cerium oxide, Au/Al2O3Phosphotungstic acid, tungstic acid, sodium tungstate and tungsten trioxide.
9. The method for preparing p-isopropylbenzaldehyde from cumene according to claim 1, wherein the method comprises the following steps: in the third step, the catalyst is tungsten trioxide.
10. A p-isopropyl benzaldehyde is characterized in that: is prepared by the preparation method of any one of claims 1 to 9.
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| GHAFFAR KH KARA ET AL.: "Preparation and characterization of perlite/V2O5 nano-spheres via a novel green method: Applied for oxidation of benzyl alcohol derivatives", 《MATERIALS CHEMISTRY AND PHYSICS》, pages 3 * |
| 施达常 等: "枯茗醇的合成研究", 《化学世界》, pages 416 * |
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