CN103145527B - Process for synthesizing p-methoxy benzaldehyde or p-tertbutyl benzaldehyde - Google Patents
Process for synthesizing p-methoxy benzaldehyde or p-tertbutyl benzaldehyde Download PDFInfo
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- CN103145527B CN103145527B CN201310064476.7A CN201310064476A CN103145527B CN 103145527 B CN103145527 B CN 103145527B CN 201310064476 A CN201310064476 A CN 201310064476A CN 103145527 B CN103145527 B CN 103145527B
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- Prior art keywords
- methoxy
- tertbutyl
- methylbenzene
- benzaldehyde
- benzoic acid
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- 238000000034 method Methods 0.000 title claims abstract description 22
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 title claims abstract description 21
- OTXINXDGSUFPNU-UHFFFAOYSA-N 4-tert-butylbenzaldehyde Chemical compound CC(C)(C)C1=CC=C(C=O)C=C1 OTXINXDGSUFPNU-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 claims abstract description 12
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 9
- QCWXDVFBZVHKLV-UHFFFAOYSA-N 1-tert-butyl-4-methylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1 QCWXDVFBZVHKLV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 238000001953 recrystallisation Methods 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 235000014493 Crataegus Nutrition 0.000 claims description 18
- 241001092040 Crataegus Species 0.000 claims description 18
- UALKQROXOHJHFG-UHFFFAOYSA-N 1-ethoxy-3-methylbenzene Chemical compound CCOC1=CC=CC(C)=C1 UALKQROXOHJHFG-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- -1 biphenyl-biphenyl ether Chemical compound 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 claims description 2
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011435 rock Substances 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 22
- 229960000583 acetic acid Drugs 0.000 abstract description 11
- 239000002351 wastewater Substances 0.000 abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 6
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 abstract description 4
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012362 glacial acetic acid Substances 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000002535 acidifier Substances 0.000 abstract 1
- 229940011182 cobalt acetate Drugs 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000010025 steaming Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 0 COc1c(*I)cc(*)cc1 Chemical compound COc1c(*I)cc(*)cc1 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229940080321 sodium anisate Drugs 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- AETSDHMVQHOYPB-UHFFFAOYSA-M sodium;4-methoxybenzoate Chemical compound [Na+].COC1=CC=C(C([O-])=O)C=C1 AETSDHMVQHOYPB-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012485 toluene extract Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a process for synthesizing p-methoxy benzaldehyde or p-tertbutyl benzaldehyde. The process comprises the following steps of: adding an acidifying agent glacial acetic acid and catalysts cobalt acetate and sodium bromide into p-methoxy methylbenzene or p-tertbutyl methylbenzene, introducing oxygen to perform oxidation reaction under a heating condition, and after the reaction, washing feed liquid with water for twice to remove the catalysts and the acetic acid; adding an oil phase after washing into a high-boiling-point solvent, and then performing rectification under vacuum step by step; unmixing and steaming out excessive p-methoxy methylbenzene or p-tertbutyl methylbenzene, then increasing the vacuum degree and the temperature, and collecting a gas-phase condensate to obtain the p-methoxy benzaldehyde or p-tertbutyl benzaldehyde; and continuously raising the rectification temperature, and receiving the gas-phase condensate with water, and performing recrystallization for twice to obtain p-methoxy benzoic acid or p-tertbutyl benzoic acid. According to the process, the discharge of waste water is reduced, the generation of the waste water containing sodium sulfate is avoided, and meanwhile, methylbenzene is not used for extracting the p-methoxy benzoic acid or p-tertbutyl benzoic acid, so that the pollution of the methylbenzene to the environment is reduced.
Description
Technical field
The present invention relates to replace the method that toluene oxidation is prepared substituted benzaldehyde.
Background technology
Taking to methoxy toluene or p-tert-butyltoluene as raw material, synthetic aubepine or p-t-Butylbenzaldehyde coproduction are identical to the technique of methoxyl group or p-tert-butyl benzoic acid, only processing parameter is slightly variant, its technological process comprise oxidizing reaction, distillation remove acetic acid, washing alkali cleaning, to several steps such as methoxyl group or p-tert-butyl benzoic acid separation, aubepine or p-t-Butylbenzaldehyde rectifying separation.Taking aubepine as example, its reaction formula is as follows.
Enough to methoxy toluene after acidifying with acetic acid, add catalyzer Sodium Bromide and Cobaltous diacetate, logical oxygen carries out oxidizing reaction at a certain temperature, generates aubepine and anisic acid.Synthetic feed liquid removes acetic acid, washs and remove catalyzer through distillation, then through sodium carbonate alkali cleaning, makes the anisic acid generating become sodium anisate to separate with organic phase.Organic phase is the excessive aubepine that methoxy toluene is being dissolved, and separates aubepine through rectification under vacuum, remaining methoxy toluene is returned to synthesis unit.
Soda ash alkali cleaning water containing sodium anisate, obtains anisic acid and sodium sulfate through sulfuric acid neutralization, adds that toluene extracts, layering.Water is contains sodium sulfate waste water.Oil phase is through precipitation, decrease temperature crystalline, and the centrifugal anisic acid wet product that obtains, dries to obtain qualified anisic acid.Centrifuge mother liquor Distillation recovery toluene, applies mechanically.Fig. 1 is shown in technical process.
This technique sepn process complexity, except synthetic wastewater, also produces a great deal of contains sodium sulfate high-concentration waste water, contains toluene non-condensable gas etc., and toluene unit consumption is about 0.068t/t,
Summary of the invention
The present invention intends selecting high boiling organic solvent, adopts substep rectification process, successively isolates methoxy toluene, aubepine and anisic acid, simplifies separating technology, no longer consumes toluene extraction, and has eliminated the generation of contains sodium sulfate waste water.
Technical scheme of the present invention is as follows:
The synthesis technique of a kind of aubepine or p-t-Butylbenzaldehyde, its technical process is shown in, Fig. 2, will be to methoxy toluene, acidifying with acetic acid on the rocks and catalyst acetic acid cobalt and Sodium Bromide, under heating condition, logical oxygen carries out oxidizing reaction, after reaction finishes, wash at twice feed liquid with water, to remove catalyzer and acetic acid, oil phase after washing adds the high boiling organic solvent of boiling point more than 330 DEG C, then carry out step-by-step decompression rectifying, first at-0.09MPa, 85-90 DEG C of precipitation steams excessive to methoxy toluene or at-0.09MPa, 80-86 DEG C of precipitation steams excessive p-tert-butyltoluene, then gas clean-up and temperature, under-0.098MPa, collecting vapor condensation thing at 100-105 DEG C obtains aubepine or collects vapor condensation thing at 98-104 DEG C obtaining p-t-Butylbenzaldehyde, continue to improve rectification temperature, under-0.098MPa, steam anisic acid or steam p-tert-butyl benzoic acid at 114-118 DEG C at 118-123 DEG C, water is accepted vapor condensation thing and through twice recrystallization, obtain anisic acid or p-tert-butyl benzoic acid.
Above-mentioned aubepine or the synthesis technique of p-t-Butylbenzaldehyde, the high boiling organic solvent of described boiling point more than 330 DEG C can be methyl diphenyl or biphenyl-biphenyl ether.
Aubepine of the present invention or p-t-Butylbenzaldehyde synthesis technique have reduced the discharge of waste water, avoid the generation of contains sodium sulfate waste water, meanwhile, without toluene extraction anisic acid or p-tert-butyl benzoic acid, reduced the pollution of toluene to environment.
Brief description of the drawings
Fig. 1 is the flow process of the synthesis technique of the aubepine of prior art;
Fig. 2 is the flow process of the synthesis technique of aubepine of the present invention.
Embodiment
Further illustrate the present invention with embodiment below.
Embodiment 1
In 1000mL reaction flask, add methoxy toluene 525mL, Glacial acetic acid 150mL, Cobaltous diacetate 50g and Sodium Bromide 30g, stir, be heated to 45 DEG C, logical oxygen 4h reaction finishes; The 800mL washing reaction feed liquid that adds water at twice, to remove catalyzer and acetic acid.
Oil phase after washing adds monomethyl biphenyl 200mL, mixes, and decompression precipitation (0.09MPa, 85-90 DEG C), removes methoxy toluene; Continue to improve rectification temperature (0.098MPa, 100-105 DEG C), vapor condensation obtains aubepine (light yellow liquid, acid number :≤1.0mgKOH/g, content 99.3%); Again improve rectification temperature (0.098MPa, 118-123 DEG C), steam anisic acid, the anisic acid of gas phase passes into water absorption tower, cooling crystallization, after recrystallization, oven dry, obtain anisic acid (white powder crystallization, melting range 181-185 DEG C, content 99.2%).
Embodiment 2
In 1000mL reaction flask, add p-tert-butyltoluene 700mL, Glacial acetic acid 20mL, Cobaltous diacetate 10g and Sodium Bromide 4.5g, stir, be heated to 45 DEG C, logical oxygen 4h reaction finishes; The 1000mL washing reaction feed liquid that adds water at twice, to remove catalyzer and acetic acid.
Oil phase after washing adds 260mL biphenyl-biphenyl ether eutectic mixture, mixes, and the precipitation that reduces pressure (0.09MPa, 80-86 DEG C), removes excessive p-tert-butyltoluene; Continue to improve rectification temperature (0.098MPa, 98-104 DEG C), vapor condensation obtains p-t-Butylbenzaldehyde (light yellow liquid, content 99.2%); Again improve rectification temperature (0.098MPa, 114-118 DEG C), remove p-tert-butyl benzoic acid, the p-tert-butyl benzoic acid of gas phase passes into water absorption tower, cooling crystallization, after recrystallization, oven dry, obtain p-tert-butyl benzoic acid (white powder crystallization, 164.0～166.0 DEG C of melting ranges, content 99.05%).
Claims (2)
1. the synthesis technique of an aubepine or p-t-Butylbenzaldehyde, will be to methoxy toluene or p-tert-butyltoluene, acidifying with acetic acid on the rocks and catalyst acetic acid cobalt and Sodium Bromide, under heating condition, logical oxygen carries out oxidizing reaction, after reaction finishes, wash at twice feed liquid with water, to remove catalyzer and acetic acid, it is characterized in that: the oil phase after washing adds the high boiling organic solvent of boiling point more than 330 DEG C, then carry out step-by-step decompression rectifying, first at-0.09MPa, 85-90 DEG C of precipitation steams excessive to methoxy toluene or at-0.09MPa, 80-86 DEG C of precipitation steams excessive p-tert-butyltoluene, then gas clean-up and temperature, under-0.098MPa, collecting vapor condensation thing at 100-105 DEG C obtains aubepine or collects vapor condensation thing at 98-104 DEG C obtaining p-t-Butylbenzaldehyde, continue to improve rectification temperature, under-0.098MPa, steam anisic acid or steam p-tert-butyl benzoic acid at 114-118 DEG C at 118-123 DEG C, water receives vapor condensation thing through twice recrystallization, obtain anisic acid or p-tert-butyl benzoic acid.
2. according to the synthesis technique of the aubepine described in claim 1 or p-t-Butylbenzaldehyde, it is characterized in that: the high boiling organic solvent of described boiling point more than 330 DEG C is monomethyl biphenyl or biphenyl-biphenyl ether.
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| CN201310064476.7A CN103145527B (en) | 2013-02-28 | 2013-02-28 | Process for synthesizing p-methoxy benzaldehyde or p-tertbutyl benzaldehyde |
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| CN201310064476.7A CN103145527B (en) | 2013-02-28 | 2013-02-28 | Process for synthesizing p-methoxy benzaldehyde or p-tertbutyl benzaldehyde |
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| CN103145527A CN103145527A (en) | 2013-06-12 |
| CN103145527B true CN103145527B (en) | 2014-12-10 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237317B (en) * | 2015-10-28 | 2017-05-10 | 江西科苑生物药业有限公司 | Combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid |
| CN106673985A (en) * | 2015-11-09 | 2017-05-17 | 宁夏际华环境安全科技有限公司 | Production process of p-methoxybenzyl alcohol |
| CN109772466B (en) * | 2019-01-23 | 2021-12-24 | 厦门中坤化学有限公司 | Method for recovering cobalt acetate/sodium bromide catalyst in catalytic oxidation reaction |
| CN113527074B (en) * | 2021-09-01 | 2022-11-04 | 湖北师范大学 | Method for preparing anisic aldehyde by continuously catalyzing and oxidizing p-methyl anisole through micro-channel |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1166480A (en) * | 1996-05-17 | 1997-12-03 | 东丽株式会社 | Method for preparing aromatic carboxylic acids, aromatic aldehydes, and aromatic alcohols |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1166480A (en) * | 1996-05-17 | 1997-12-03 | 东丽株式会社 | Method for preparing aromatic carboxylic acids, aromatic aldehydes, and aromatic alcohols |
Non-Patent Citations (2)
| Title |
|---|
| 柳艳修等.甲苯直接氧化制苯甲醛研究进展.《工业催化》.2005,第13卷(第2期),第24-28页. * |
| 甲苯直接氧化制苯甲醛研究进展;柳艳修等;《工业催化》;20050228;第13卷(第2期);第24-28页 * |
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