CN105622428A - Preparation method of 3-methyl-4-isopropylaniline - Google Patents
Preparation method of 3-methyl-4-isopropylaniline Download PDFInfo
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- CN105622428A CN105622428A CN201610081470.4A CN201610081470A CN105622428A CN 105622428 A CN105622428 A CN 105622428A CN 201610081470 A CN201610081470 A CN 201610081470A CN 105622428 A CN105622428 A CN 105622428A
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- Prior art keywords
- methyl
- component
- isopropyl aniline
- preparation
- aminotoluene
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- MKYJJJUJQHKWNM-UHFFFAOYSA-N 3-methyl-4-propan-2-ylaniline Chemical compound CC(C)C1=CC=C(N)C=C1C MKYJJJUJQHKWNM-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000000746 purification Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 60
- 239000000376 reactant Substances 0.000 claims description 46
- 239000013078 crystal Substances 0.000 claims description 27
- 235000011149 sulphuric acid Nutrition 0.000 claims description 21
- 239000001117 sulphuric acid Substances 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000012043 crude product Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000012044 organic layer Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 208000035126 Facies Diseases 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 230000000994 depressogenic effect Effects 0.000 claims description 10
- 239000000284 extract Substances 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 230000002572 peristaltic effect Effects 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000011973 solid acid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 5
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 abstract 2
- 238000005804 alkylation reaction Methods 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 239000010453 quartz Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IGDKJXXPUDSVMV-UHFFFAOYSA-N 3-methyl-n-propan-2-ylaniline Chemical compound CC(C)NC1=CC=CC(C)=C1 IGDKJXXPUDSVMV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
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- 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 invention relates to a preparation method of 3-methyl-4-isopropylaniline. The preparation method includes the following steps: (1) dissolving m-toluidine in sulfuric acid solution 50-98% in mass concentration as a component 1, then adding an isopropylation reagent into another container to serve as a component 2, simultaneously feeding the component 1 and the component 2 into a jet mixer with the flow rate of 5-10:1 to be mixed at the temperature of 10-35 DEG C, and then reacting at the temperature of 60-95 DEG C through a quartz reaction tube to obtain reaction solution for alkylation reaction; (2) subjecting the reaction solution obtained in the step (1) to separation and purification to obtain 3-methyl-4-isopropylaniline. The 3-methyl-4-isopropylaniline prepared through the method has the advantages of mild reaction condition, high yield, few by-products, less pollution and the like, and the problems of a lot of by-products, strict conditions and severe pollution in the preparation process of the 3-methyl-4-isopropylaniline in the prior art are solved effectively.
Description
Technical field
The preparation method that the present invention relates to a kind of organic intermediate, the preparation method especially relating to the 3-methyl-4-isopropyl aniline of a kind of high-quality.
Background technology
3-methyl-4-isopropyl aniline is a kind of important organic intermediate, is widely used in the field such as medicine, dyestuff. At present, the method for preparation synthesis 3-methyl-4-isopropyl aniline is not also overripened, and existing method prepare 3-methyl-4-isopropyl aniline, substantially all still in the laboratory lab scale stage, fails to realize industrialized production.
Existing report mainly has two kinds of methods preparing 3-methyl-4-isopropyl aniline, first method is with meta-aminotoluene for raw material, under the effect of concentrated sulphuric acid, carry out Friedel-Crafts reaction with isopropanol or 2 cbloropropane isopropyl chloride for isopropylating agent and obtain 3-methyl-4-isopropyl aniline, the method not only selectivity is poor, and the low unfavorable industrialized production of production capacity; Second method is with N-isopropyl-3-monomethylaniline. for raw material, obtains 3-methyl-4-isopropyl aniline by rearrangement under basic conditions, and the method yield is low, and raw material is difficult to obtain, and is not suitable for industrialized production.
Summary of the invention
For the deficiency overcoming prior art to exist, the preparation method that the invention provides a kind of 3-methyl-4-isopropyl aniline, use the method can controlled syntheses 3-methyl-4-isopropyl aniline, have the advantages that yield high pollution is little, solving 3-methyl-4-isopropyl aniline, to prepare yield low, the problem that by-product is many.
The preparation method of a kind of 3-methyl-4-isopropyl aniline, comprises the steps:
(1) meta-aminotoluene is dissolved in the sulfuric acid solution that mass concentration is 50��98% as component 1, then in another container, isopropylating agent is added as component 2, component 1 and component 2 are simultaneously entered in jet mixer at 10��35 DEG C according to the flow velocity of 5��10:1 and mix, be obtained by reacting the reactant liquor of alkylated reaction again through the crystal reaction tube being filled with solid acid catalyst at 60��95 DEG C;
(2) the separated purification of reactant liquor that step (1) obtains obtains 3-methyl-4-isopropyl aniline.
Its synthetic route is:
The present invention with meta-aminotoluene for raw material, the Friedel-Crafts reaction being filled through in the crystal reaction tube of solid acid catalyst carrying out, prepare the 3-methyl-4-isopropyl aniline of high-quality after purification. Present invention process is simple, and product post processing is easy, and environmental pollution is little, and the 3-methyl-4-isopropyl aniline product quality that relatively additive method prepares is high, good stability.
As preferably, in step (1), sulfuric acid solution and the weight ratio of meta-aminotoluene after folding hundred are 4��12:1; Described isopropylating agent is the one in isopropanol, 2 cbloropropane isopropyl chloride or 2-N-Propyl Bromide, and the weight ratio of isopropylating agent and meta-aminotoluene is 1��3:1. Wherein, sulfuric acid solution as solvent be not involved in reaction.
As preferably, in step (1), described jet mixer is multistage T-shaped jet mixer, and mixing temperature controls at 20��30 DEG C; Component 1 and component 2 charging rate weight ratio (linear velocity) are 6.0��8.0:1.
As preferably, in step (1), the caliber 2��5mm of described crystal reaction tube, pipe range is 1��5m; Reaction temperature in crystal reaction tube is 70��90 DEG C, and the time of staying is 10��45s.
As preferably, in step (1), the solid acid in crystal reaction tube is the solid super-strong acid containing sulfate radical, and its carrier is one or more the combination in any in iron sesquioxide, zirconium dioxide, titanium dioxide.
As preferably, described solid acid catalyst processes through molding, granulating, and its particle diameter is 0.2��1.0mm.
As preferably, in step (2), the method of reactant liquor separation purification is: reactant liquor is down to 10��30 DEG C, after alkaline solution adjustment reacting liquid pH value to 7��10, filter, filtrate organic solvent extraction, take organic layer concentrating under reduced pressure after washing and remove solvent, take concentrate and carry out rectification process, collect the fraction of 130��140 DEG C, obtain 3-methyl-4-isopropyl aniline.
As preferably, described alkaline solution is organic base aqueous solution or inorganic base aqueous solution.
As preferably, the preparation method of described 3-methyl-4-isopropyl aniline, comprise the steps:
(1) being joined in four-hole bottle by the sulfuric acid solution that 1900.0g mass concentration is 95%, stirring is cooled to 0��10 DEG C, drips meta-aminotoluene 214.3g, dropping process temperature is maintained between 0��10 DEG C, controls 2h and is added dropwise to complete, finishes, continue stirring 30min, standby as component 1; Then in another flask, 2 cbloropropane isopropyl chloride 300.0g is added as component 2; With peristaltic pump component 1 and component 2, being input simultaneously in T-shaped jet mixer to mix by the flow velocity of 7:1, mixing temperature controls at 20��30 DEG C; Then it is depressed in the zirconium oxide crystal reaction tube equipped with 6.0g load sulphuric acid, is obtained by reacting the reactant liquor of alkylated reaction at 80��85 DEG C; Wherein, the caliber of crystal reaction tube is 2.5mm, and pipe range is 2.0m, and the time of staying is 28s, and the zirconium oxide particle diameter of load sulphuric acid is 0.5mm;
(2) reactant liquor ice-water bath is down to 20 DEG C, then the ammonia dripping mass concentration 25% regulates reactant liquor pH to 8, solids removed by filtration salt, filter cake 100ml ethyl acetate rinses, merge rinsing liquid and filtrate and extract by 400ml �� 2 ethyl acetate, separatory, taking organic layer 500ml and wash twice, organic facies concentration removes solvent, obtains the crude product of 3-methyl-4-isopropyl aniline; The crude product of 3-methyl-4-isopropyl aniline carries out rectification, vacuum 50��60mmHg, and the fraction between collecting 90��100 DEG C is raw material meta-aminotoluene, and the fraction between collecting 130��140 DEG C is 3-methyl-4-isopropyl aniline.
Compared with prior art, the beneficial effects are mainly as follows: adopt method provided by the invention to prepare 3-methyl-4-isopropyl aniline, have reaction condition gentleness, yield is high, by-product is few, pollute the features such as little, effectively solves in existing 3-methyl-4-isopropyl aniline preparation process that by-product is many, condition is harsh, a heavy-polluted difficult problem.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but invention which is intended to be protected is not limited to this.
Embodiment 1
1900.0g sulfuric acid solution (95wt%) is joined in four-hole bottle, stirring is cooled between 0��10 DEG C, dropping meta-aminotoluene 214.3g, dropping process temperature is maintained between 0��10 DEG C, control 2h to be added dropwise to complete, finish, continue stirring 30min, standby as component 1, another flask adds 2 cbloropropane isopropyl chloride 300.0g as component 2, with peristaltic pump component 1 and component 2, it is input simultaneously in T-shaped jet mixer quickly mix at 20 DEG C by the flow velocity (charging rate weight ratio) of 7:1, then it is depressed into equipped with in the zirconium oxide crystal reaction tube (microreactor) of 6.0g load sulphuric acid, the reactant liquor of alkylated reaction it is obtained by reacting at 80��85 DEG C, the caliber 2.5mm of crystal reaction tube, pipe range is 2.0m, and the time of staying is 28s, and the zirconium oxide particle diameter of load sulphuric acid is 0.5mm, reactant liquor is received with the four-hole bottle of 3L.
Treat that component 1 and component 2 have all been pressed, reactant liquor ice-water bath is down to 20 DEG C, then the ammonia dripping mass concentration 25% regulates reactant liquor pH to 8, solids removed by filtration salt, filter cake 100ml ethyl acetate rinses, and merges rinsing liquid and filtrate and extracts by 400ml �� 2 ethyl acetate, separatory, taking organic layer 500ml to wash twice, organic facies concentration removes solvent, obtains the crude product of 3-methyl-4-isopropyl aniline.
The crude product rectification (vacuum 50��60mmHg) of 3-methyl-4-isopropyl aniline, fraction between collecting 90��100 DEG C is raw material meta-aminotoluene, fraction between collecting 130��140 DEG C is 3-methyl-4-isopropyl aniline, collected fraction detects through GC, first fraction (i.e. meta-aminotoluene) purity 98.8%, can direct reuse, collect 12g, second fraction (i.e. 3-methyl-4-isopropyl aniline) GC purity 99.2%, 250g, it is 91.1% according to the meta-aminotoluene meter product yield converted, the meta-aminotoluene response rate 5.6%.
Embodiment 2
2300.0g sulfuric acid solution (80wt%) is joined in four-hole bottle, stirring is cooled between 0��10 DEG C, dropping meta-aminotoluene 214.3g, dropping process temperature is maintained between 0��10 DEG C, control 2h to be added dropwise to complete, finish, continue stirring 30min, standby as component 1, another flask adds isopropanol 250g as component 2, with peristaltic pump component 1 and component 2, it is input simultaneously in T-shaped jet mixer quickly mix at 30 DEG C by the flow velocity of 10:1, then it is depressed in the zirconium oxide crystal reaction tube equipped with 6.0g load sulphuric acid, the reactant liquor of alkylated reaction it is obtained by reacting at 85��90 DEG C, the caliber 5mm of crystal reaction tube, pipe range is 5m, and the time of staying is 40s, and the zirconium oxide particle diameter of load sulphuric acid is 1.0mm, reactant liquor is received with the four-hole bottle of 3L.
Treat that component 1 and component 2 have all been pressed, reactant liquor ice-water bath is down to 30 DEG C, then the ammonia dripping mass concentration 25% regulates reactant liquor pH to 9, solids removed by filtration salt, filter cake 100ml ethyl acetate rinses, and merges rinsing liquid and filtrate and extracts by 400ml �� 2 ethyl acetate, separatory, taking organic layer 500ml to wash twice, organic facies concentration removes solvent, obtains the crude product of 3-methyl-4-isopropyl aniline.
The crude product rectification (vacuum 50��60mmHg) of 3-methyl-4-isopropyl aniline, fraction between collecting 90��100 DEG C is raw material meta-aminotoluene, fraction between collecting 130��140 DEG C is 3-methyl-4-isopropyl aniline, collected fraction detects through GC, first fraction (i.e. meta-aminotoluene) purity 98%, can direct reuse, collect 34g, second fraction (i.e. 3-methyl-4-isopropyl aniline) GC purity 96.2%, 228g, it is 83.2% according to the meta-aminotoluene meter product yield converted, the meta-aminotoluene response rate about 15.9%.
Embodiment 3
2000.0g sulfuric acid solution (85wt%) is joined in four-hole bottle, stirring is cooled between 0��10 DEG C, dropping meta-aminotoluene 214.3g, dropping process temperature is maintained between 0��10 DEG C, control 2h to be added dropwise to complete, finish, continue stirring 30min, standby as component 1, another flask adds isopropanol 220g as component 2, with peristaltic pump component 1 and component 2, being input simultaneously in T-shaped jet mixer quickly mix by the flow velocity (charging rate weight ratio) of 9:1, mixing temperature controls at 25 DEG C; Then it is depressed in the zirconium oxide crystal reaction tube equipped with 6.0g load sulphuric acid, is obtained by reacting the reactant liquor of alkylated reaction at 70��75 DEG C; The caliber 2.5mm of microreactor, pipe range is 2.0m, and the time of staying is 25s, and the zirconium oxide particle diameter of load sulphuric acid is 0.2mm; Reactant liquor is received with the four-hole bottle of 3L.
Treat that component 1 and component 2 have all been pressed, reactant liquor ice-water bath is down to 10 DEG C, then the ammonia dripping mass concentration 25% regulates reactant liquor pH to 7, solids removed by filtration salt, filter cake 100ml ethyl acetate rinses, and merges rinsing liquid and filtrate and extracts by 400ml �� 2 ethyl acetate, separatory, taking organic layer 500ml to wash twice, organic facies concentration removes solvent, obtains the crude product of 3-methyl-4-isopropyl aniline.
The crude product rectification (vacuum 50��60mmHg) of 3-methyl-4-isopropyl aniline, fraction between collecting 90��100 DEG C is raw material meta-aminotoluene, fraction between collecting 130��140 DEG C is 3-methyl-4-isopropyl aniline, collected fraction detects through GC, first fraction (i.e. meta-aminotoluene) purity 93.7%, can direct reuse, collect 27g, second fraction (i.e. 3-methyl-4-isopropyl aniline) GC purity 97.6%, 227g, it is 82.7% according to the meta-aminotoluene meter product yield converted, the meta-aminotoluene response rate 12.6%.
Embodiment 4
1800.0g sulfuric acid solution (75wt%) is joined in four-hole bottle, stirring is cooled between 0��10 DEG C, dropping meta-aminotoluene 214.3g, dropping process temperature is maintained between 0��10 DEG C, control 2h to be added dropwise to complete, finish, continue stirring 30min, standby as component 1, another flask adds 2-N-Propyl Bromide 350g as component 2, with peristaltic pump component 1 and component 2, being input simultaneously in T-shaped jet mixer quickly mix by the flow velocity (charging rate weight ratio) of 6:1, mixing temperature controls at 35 DEG C; Then it is depressed into equipped with in the titanium dioxide crystal reaction tube (microreactor) of 6.0g load sulphuric acid, is obtained by reacting the reactant liquor of alkylated reaction at 70��75 DEG C; The caliber 2.5mm of microreactor, pipe range is 2.0m, and the time of staying is 25s, and the titanium dioxide particle diameter of load sulphuric acid is 0.8mm; Reactant liquor is received with the four-hole bottle of 3L.
Treat that component 1 and component 2 have all been pressed, reactant liquor ice-water bath is down to 10 DEG C, then the ammonia dripping mass concentration 25% regulates reactant liquor pH to 8.5, solids removed by filtration salt, filter cake 100ml ethyl acetate rinses, and merges rinsing liquid and filtrate and extracts by 400ml �� 2 ethyl acetate, separatory, taking organic layer 500ml to wash twice, organic facies concentration removes solvent, obtains the crude product of 3-methyl-4-isopropyl aniline.
The crude product rectification (vacuum 50��60mmHg) of 3-methyl-4-isopropyl aniline, fraction between collecting 90��100 DEG C is raw material meta-aminotoluene, fraction between collecting 130��140 DEG C is 3-methyl-4-isopropyl aniline, collected fraction detects through GC, first fraction (i.e. meta-aminotoluene) purity 92.9%, can direct reuse, collect 35g, second fraction (i.e. 3-methyl-4-isopropyl aniline) GC purity 96.5%, 222g, it is 80.8% according to the meta-aminotoluene meter product yield converted, the meta-aminotoluene response rate 16.3%.
Embodiment 5
1500.0g sulfuric acid solution (95wt%) is joined in four-hole bottle, stirring is cooled between 0��10 DEG C, dropping meta-aminotoluene 214.3g, dropping process temperature is maintained between 0��10 DEG C, control 2h to be added dropwise to complete, finish, continue stirring 30min, standby as component 1, another flask adds 2 cbloropropane isopropyl chloride 400g as component 2, with peristaltic pump component 1 and component 2, it is input simultaneously in T-shaped jet mixer quickly mix at 30 DEG C by the flow velocity of 8:1, then it is depressed in the iron sesquioxide crystal reaction tube equipped with 6.0g load sulphuric acid, the reactant liquor of alkylated reaction it is obtained by reacting at 85��90 DEG C, the caliber 5mm of crystal reaction tube, pipe range is 5m, and the time of staying is 30s, and the iron sesquioxide particle diameter of load sulphuric acid is 0.6mm, reactant liquor is received with the four-hole bottle of 3L.
Treat that component 1 and component 2 have all been pressed, reactant liquor ice-water bath is down to 25 DEG C, then the ammonia dripping mass concentration 25% regulates reactant liquor pH to 9, solids removed by filtration salt, filter cake 100ml ethyl acetate rinses, and merges rinsing liquid and filtrate and extracts by 400ml �� 2 ethyl acetate, separatory, taking organic layer 500ml to wash twice, organic facies concentration removes solvent, obtains the crude product of 3-methyl-4-isopropyl aniline.
The crude product rectification (vacuum 50��60mmHg) of 3-methyl-4-isopropyl aniline, fraction between collecting 90��100 DEG C is raw material meta-aminotoluene, fraction between collecting 130��140 DEG C is 3-methyl-4-isopropyl aniline, collected fraction detects through GC, first fraction (i.e. meta-aminotoluene) purity 96.7%, can direct reuse, collect 30g, second fraction (i.e. 3-methyl-4-isopropyl aniline) GC purity 96.9%, 216g, it is 78.8% according to the meta-aminotoluene meter product yield converted, the meta-aminotoluene response rate about 14%.
Embodiment 6
2200.0g sulfuric acid solution (90wt%) is joined in four-hole bottle, stirring is cooled between 0��10 DEG C, dropping meta-aminotoluene 214.3g, dropping process temperature is maintained between 0��10 DEG C, control 2h to be added dropwise to complete, finish, continue stirring 30min, standby as component 1, another flask adds 2 cbloropropane isopropyl chloride 230.0g as component 2, with peristaltic pump component 1 and component 2, it is input simultaneously in T-shaped jet mixer quickly mix at 15 DEG C by the flow velocity of 6:1, then it is depressed in the titanium dioxide crystal reaction tube equipped with 6.0g load sulphuric acid, the reactant liquor of alkylated reaction it is obtained by reacting at 80��85 DEG C, the caliber 2.5mm of crystal reaction tube, pipe range is 2.0m, and the time of staying is 32s, and the titanium dioxide particle diameter of load sulphuric acid is 0.7mm, reactant liquor is received with the four-hole bottle of 3L.
Treat that component 1 and component 2 have all been pressed, reactant liquor ice-water bath is down to 20 DEG C, then the ammonia dripping mass concentration 25% regulates reactant liquor pH to 8, solids removed by filtration salt, filter cake 100ml ethyl acetate rinses, and merges rinsing liquid and filtrate and extracts by 400ml �� 2 ethyl acetate, separatory, taking organic layer 500ml to wash twice, organic facies concentration removes solvent, obtains the crude product of 3-methyl-4-isopropyl aniline.
The crude product rectification (vacuum 50��60mmHg) of 3-methyl-4-isopropyl aniline, fraction between collecting 90��100 DEG C is raw material meta-aminotoluene, fraction between collecting 130��140 DEG C is 3-methyl-4-isopropyl aniline, collected fraction detects through GC, first fraction (i.e. meta-aminotoluene) purity 97.1%, can direct reuse, collect 10g, second fraction (i.e. 3-methyl-4-isopropyl aniline) GC purity 97.9%, 220g, it is 80.2% according to the meta-aminotoluene meter product yield converted, the meta-aminotoluene response rate 4.7%.
Embodiment 7
2500.0g sulfuric acid solution (85wt%) is joined in four-hole bottle, stirring is cooled between 0��10 DEG C, dropping meta-aminotoluene 214.3g, dropping process temperature is maintained between 0��10 DEG C, control 2h to be added dropwise to complete, finish, continue stirring 30min, standby as component 1, another flask adds isopropanol 500.0g as component 2, with peristaltic pump component 1 and component 2, it is input simultaneously in T-shaped jet mixer quickly mix at 20 DEG C by the flow velocity of 7:1, then it is depressed in the zirconium oxide crystal reaction tube equipped with 6.0g load sulphuric acid, the reactant liquor of alkylated reaction it is obtained by reacting at 80��85 DEG C, the caliber 2.5mm of crystal reaction tube, pipe range is 2.0m, and the time of staying is 25s, and the zirconium oxide particle diameter of load sulphuric acid is 0.4mm, reactant liquor is received with the four-hole bottle of 3L.
Treat that component 1 and component 2 have all been pressed, reactant liquor ice-water bath is down to 20 DEG C, then the ammonia dripping mass concentration 25% regulates reactant liquor pH to 8, solids removed by filtration salt, filter cake 100ml ethyl acetate rinses, and merges rinsing liquid and filtrate and extracts by 400ml �� 2 ethyl acetate, separatory, taking organic layer 500ml to wash twice, organic facies concentration removes solvent, obtains the crude product of 3-methyl-4-isopropyl aniline.
The crude product rectification (vacuum 50��60mmHg) of 3-methyl-4-isopropyl aniline, fraction between collecting 90��100 DEG C is raw material meta-aminotoluene, fraction between collecting 130��140 DEG C is 3-methyl-4-isopropyl aniline, collected fraction detects through GC, first fraction (i.e. meta-aminotoluene) purity 93.2%, can direct reuse, collect 13g, second fraction (i.e. 3-methyl-4-isopropyl aniline) GC purity 92.9%, 206g, it is 75.1% according to the meta-aminotoluene meter product yield converted, the meta-aminotoluene response rate 6.1%.
Embodiment 8
1200.0g sulfuric acid solution (85wt%) is joined in four-hole bottle, stirring is cooled between 0��10 DEG C, dropping meta-aminotoluene 214.3g, dropping process temperature is maintained between 0��10 DEG C, control 2h to be added dropwise to complete, finish, continue stirring 30min, standby as component 1, another flask adds isopropanol 300.0g as component 2, with peristaltic pump component 1 and component 2, it is input simultaneously in T-shaped jet mixer quickly mix at 20 DEG C by the flow velocity of 7:1, then it is depressed in the zirconium oxide crystal reaction tube equipped with 6.0g load sulphuric acid, the reactant liquor of alkylated reaction it is obtained by reacting at 80��85 DEG C, the caliber 2.5mm of crystal reaction tube, pipe range is 2.0m, and the time of staying is 25s, and the zirconium oxide particle diameter of load sulphuric acid is 0.6mm, reactant liquor is received with the four-hole bottle of 3L.
Treat that component 1 and component 2 have all been pressed, reactant liquor ice-water bath is down to 20 DEG C, then the ammonia dripping mass concentration 25% regulates reactant liquor pH to 8, solids removed by filtration salt, filter cake 100ml ethyl acetate rinses, and merges rinsing liquid and filtrate and extracts by 400ml �� 2 ethyl acetate, separatory, taking organic layer 500ml to wash twice, organic facies concentration removes solvent, obtains the crude product of 3-methyl-4-isopropyl aniline.
The crude product rectification (vacuum 50��60mmHg) of 3-methyl-4-isopropyl aniline, fraction between collecting 90��100 DEG C is raw material meta-aminotoluene, fraction between collecting 130��140 DEG C is 3-methyl-4-isopropyl aniline, collected fraction detects through GC, first fraction (i.e. meta-aminotoluene) purity 94.1%, can direct reuse, collect 16g, second fraction (i.e. 3-methyl-4-isopropyl aniline) GC purity 93.2%, 202g, it is 73.6% according to the meta-aminotoluene meter product yield converted, the meta-aminotoluene response rate 7.5%.
Claims (9)
1. a preparation method for 3-methyl-4-isopropyl aniline, its feature is comprising the steps:
(1) meta-aminotoluene is dissolved in the sulfuric acid solution that mass concentration is 50��98% as component 1, then in another container, isopropylating agent is added as component 2, component 1 and component 2 are simultaneously entered in jet mixer at 10��35 DEG C according to the flow velocity of 5��10:1 and mix, be obtained by reacting the reactant liquor of alkylated reaction again through the crystal reaction tube being filled with solid acid catalyst at 60��95 DEG C;
(2) the separated purification of reactant liquor that step (1) obtains obtains 3-methyl-4-isopropyl aniline.
2. the preparation method of 3-methyl-4-isopropyl aniline according to claim 1, it is characterised in that: in step (1), sulfuric acid solution and the weight ratio of meta-aminotoluene after folding hundred are 4��12:1; Described isopropylating agent is the one in isopropanol, 2 cbloropropane isopropyl chloride or 2-N-Propyl Bromide, and the weight ratio of isopropylating agent and meta-aminotoluene is 1��3:1.
3. the preparation method of 3-methyl-4-isopropyl aniline according to claim 1, it is characterised in that: in step (1), described jet mixer is multistage T-shaped jet mixer, and mixing temperature controls at 20��30 DEG C; Component 1 and component 2 charging rate weight ratio are 6.0��8.0:1.
4. the preparation method of 3-methyl-4-isopropyl aniline according to claim 1, it is characterised in that: in step (1), the caliber 2��5mm of described crystal reaction tube, pipe range is 1��5m; Reaction temperature in crystal reaction tube is 70��90 DEG C, and the time of staying is 10��45s.
5. the preparation method of 3-methyl-4-isopropyl aniline according to claim 1, it is characterized in that: in step (1), solid acid in crystal reaction tube is the solid super-strong acid containing sulfate radical, and its carrier is one or more the combination in any in iron sesquioxide, zirconium dioxide, titanium dioxide.
6. the preparation method of 3-methyl-4-isopropyl aniline according to claim 5, it is characterised in that: described solid acid catalyst processes through molding, granulating, and its particle diameter is 0.2��1.0mm.
7. the preparation method of 3-methyl-4-isopropyl aniline according to claim 1, it is characterized in that: in step (2), the method of reactant liquor separation purification is: reactant liquor is down to 10��30 DEG C, after alkaline solution adjustment reacting liquid pH value to 7��10, filter, filtrate organic solvent extraction, take organic layer concentrating under reduced pressure after washing and remove solvent, take concentrate and carry out rectification process, collect the fraction of 130��140 DEG C, obtain 3-methyl-4-isopropyl aniline.
8. the preparation method of 3-methyl-4-isopropyl aniline according to claim 7, it is characterised in that: described alkaline solution is organic base aqueous solution or inorganic base aqueous solution.
9. the preparation method of 3-methyl-4-isopropyl aniline according to claim 1, it is characterised in that comprise the steps:
(1) being joined in four-hole bottle by the sulfuric acid solution that 1900.0g mass concentration is 95%, stirring is cooled to 0��10 DEG C, drips meta-aminotoluene 214.3g, dropping process temperature is maintained between 0��10 DEG C, controls 2h and is added dropwise to complete, finishes, continue stirring 30min, standby as component 1; Then in another flask, 2 cbloropropane isopropyl chloride 300.0g is added as component 2; With peristaltic pump component 1 and component 2, being input simultaneously in T-shaped jet mixer to mix by the flow velocity of 7:1, mixing temperature controls at 20��30 DEG C; Then it is depressed in the zirconium oxide crystal reaction tube equipped with 6.0g load sulphuric acid, is obtained by reacting the reactant liquor of alkylated reaction at 80��85 DEG C; Wherein, the caliber of crystal reaction tube is 2.5mm, and pipe range is 2.0m, and the time of staying is 28s, and the zirconium oxide particle diameter of load sulphuric acid is 0.5mm;
(2) reactant liquor ice-water bath is down to 20 DEG C, then the ammonia dripping mass concentration 25% regulates reactant liquor pH to 8, solids removed by filtration salt, filter cake 100ml ethyl acetate rinses, merge rinsing liquid and filtrate and extract by 400ml �� 2 ethyl acetate, separatory, taking organic layer 500ml and wash twice, organic facies concentration removes solvent, obtains the crude product of 3-methyl-4-isopropyl aniline; The crude product of 3-methyl-4-isopropyl aniline carries out rectification, vacuum 50��60mmHg, and the fraction between collecting 90��100 DEG C is raw material meta-aminotoluene, and the fraction between collecting 130��140 DEG C is 3-methyl-4-isopropyl aniline.
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