CN105418399A - Synthesis method of 2-methoxy-4-hydroxypropiophenone - Google Patents
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Abstract
The present invention discloses a synthesis method of 2-methoxy-4-hydroxypropiophenone, and belongs to the field of organic synthesis chemistry. According to the synthesis method disclosed by the present invention, the method comprises the following steps: using phenol as a raw martial; firstly adding a CH3I solution and sodium hydroxide into the phenol to generate p-methylphenol; then adding two oxides such as CaO2 and magnesium oxide into the p-methylphenol to generate p-hydroxybenzaldehyde; then adding a bromine solution and HAC into the p-hydroxybenzaldehyde to further generate 2-bromo-p-hydroxybenzaldehyde; then synthesizing 2-nitro-1-(2-bromo-4-hydroxy)propenyl benzene by adding nitroethan dropwise; adding a solution of Fe and HCl into the 2-nitro-1-(2-bromo-4-hydroxy)propenyl benzene to generate 2-bromo-4-hydroxypropiophenone; and finally adding methanol and PCl3 to finally generate the 2-methoxy-4-hydroxypropiophenone disclosed by the present invention. The embodiment demonstrates that the method disclosed by the present invention is not only simple in operation and low in production cost, but also has a relatively mild reaction process, and the recovery rate is significantly improved and reaches up to more than 85%.
Description
Technical field
The invention discloses a kind of synthetic method of 2-methoxyl group-4-hydroxypropiophenonepreparation, belong to organic conjunction chemical field.
Background technology
4-hydroxypropiophenonepreparation is ethyl-para-hydroxyphenyl ketone again, (English name 4-Hydroxypropiophenone) is as an important intermediate in Chemical Manufacture, in the Chemical Manufacture such as medicine and agricultural chemicals, have purposes widely, be the intermediate of the medicine such as ritodrine, Tolperisone necessity.
About the synthesis of ethyl-para-hydroxyphenyl ketone, all have relevant report both at home and abroad, synthesis mainly contains following three kinds of methods:
1, the people such as Lota, RK reports that generate ethyl-para-hydroxyphenyl ketone through Friedel-Crafts reaction, although this method a step can obtain target product, yield is lower, only has 50% with phenol and propionyl chloride for raw material in the literature; 2, the people such as Devis, R is at document Bull.Soc.Chim.Fr., (9), in 3185 – 3190 (1967) with phenol and propionic acid for raw material, generate ethyl-para-hydroxyphenyl ketone through Nencki reaction, the reactive behavior of propionic acid is lower, and yield has no report; 3, the people such as Miller, E is at document OrganicSyntheses, and 1943, report with phenylpropionate to be raw material in 2:543-545, be that catalyzer carries out Fries rearrangement generation ethyl-para-hydroxyphenyl ketone with AlCl3, but document yield is only 34% ~ 39%, and the oil of mirbane adopting toxicity large is solvent; 4, Murashige, the people such as R are at document Tetrahedron, 67,641 – 649 (2011). middle report for raw material, under triflic acid catalyzes, generates ethyl-para-hydroxyphenyl ketone through Friedel-Crafts reaction with phenol and propionyl chloride, although this method a step can obtain target product, and yield is higher, but trifluoromethanesulfonic acid is as catalyzer in Chemical Manufacture, high cost; 5, Wang Li equality people uses BF3H in " Zhejiang chemical industry " Vol.41No.1 (2010)
2o does Fries rearrangement catalyst, obtains good selectivity and yield, and reaction conditions is gentle, but catalyzer needs a large amount of input.
Summary of the invention
The technical problem that the present invention mainly solves: often there is high cost, complicated operation, by product is many and yield is lower problem for current ethyl-para-hydroxyphenyl ketone in the process of synthesis, provide a kind of synthetic method of 2-methoxyl group-4-hydroxypropiophenonepreparation.The method is starting material with phenol, first in phenol, adds CH
3i solution and sodium hydroxide generate p-methyl phenol, then in p-methyl phenol, add CaO
2with magnesium oxide two oxides thus generate p-Hydroxybenzaldehyde, bromine liquid and HAC is added again afterwards by the p-Hydroxybenzaldehyde obtained, obtained 2-bromine p-Hydroxybenzaldehyde further, subsequently by dripping the bromo-4-hydroxyl of nitroethane synthesis 2-nitro-1-(2-) phenylallene, next by the bromo-4-hydroxyl of 2-nitro-1-(2-) add Fe and HCl solution in phenylallene, the obtained bromo-4-hydroxypropiophenonepreparation of 2-, finally adds methyl alcohol and PCl again
3, a kind of 2-methoxyl group of final obtained the present invention-4-hydroxypropiophenonepreparation.Not only method is simple, and running cost reduces, and gentleer in reaction process, and yield obtains significant raising.
In order to achieve the above object, the synthetic route of 2-methoxyl group-4-hydroxypropiophenonepreparation of the present invention is:
The building-up process of the 2-methoxyl group-4-hydroxypropiophenonepreparation that the present invention relates to comprises the following steps:
(1) get 50 ~ 100g phenol and put into reactor, add the CH of 20 ~ 25 DEG C wherein
3i solution, until phenol solution is dissolved completely, adds 4 ~ 10g sodium hydroxide afterwards more wherein, after stirring, uses mixed gas to container sealing simultaneously and is forced into 0.5 ~ 0.8MPa, reacting 1 ~ 1.5h, obtain p-methyl phenol after leaving standstill at 20 ~ 40 DEG C;
(2) in the four-hole bottle of upper device agitator, prolong, dropping funnel and thermometer respectively, at normal temperatures, pour above-mentioned obtained p-methyl phenol into, and add the CaO of gained p-methyl phenol quality 0.3 ~ 0.5 times wherein
2with the magnesium oxide of 0.2 ~ 0.4 times, rapidly promote temperature to 30 ~ 35 DEG C, after stirring, fast-sealing container, in 5 ~ 10s by the pressure in container as standard atmospheric pressure, after reaction 30 ~ 45min, obtain p-Hydroxybenzaldehyde;
(3) in p-Hydroxybenzaldehyde obtained above, adding 100 ~ 150mL mass concentration is immediately the HAC solution of 37% and the bromine liquid of 80 ~ 120mL, 10 ~ 15min is left standstill after stirring, put into stirrer afterwards, arranging rotating speed is 300 ~ 400r/min, and temperature is set to 80 ~ 100 DEG C, when liquid in containers is less than 1/3 of original volume, stop rotating speed and heating, naturally cool to room temperature, 2-bromine p-Hydroxybenzaldehyde can be obtained;
(4) after the 2-bromine p-Hydroxybenzaldehyde obtained being cooled to-3 DEG C, the nitroethane of 100 ~ 120mL is dripped while stirring under negative pressure 1.2 ~ 1.5MPa, rate of addition is 2 ~ 3 per second, after being added dropwise to complete at-3 ~ 2 DEG C stirring reaction 1 ~ 2h, improving temperature is afterwards normal temperature, obtains the bromo-4-hydroxyl of 2-nitro-1-(2-after filtration) phenylallene;
(5) the bromo-4-hydroxyl of 2-nitro-1-(2-that obtains after filtering) phenylallene is positioned over after sterilization again, be equipped with in the four-hole bottle of agitator, prolong, dropping funnel and thermometer, add the Fe of 0.2 ~ 0.5g simultaneously, be heated to 105 DEG C, add with the form dripped the HCl solution that 50 ~ 60mL mass concentration is 40% more afterwards, be added dropwise to complete in 1 ~ 3min, after stirring, sealed reaction 1 ~ 2h, naturally cools to room temperature subsequently, obtains the bromo-4-hydroxypropiophenonepreparation of 2-;
(6) be 0.5 ~ 0.6MPa by bromo-for the 2-obtained 4-hydroxypropiophenonepreparation at pressure, temperature is under the condition of 105 ~ 110 DEG C, adds the CH of 30 ~ 35mL
3the PCl of OH solution and 25 ~ 50mL
3solution, and adjust ph is 5.5 ~ 6.5, after being uniformly mixed, and improves temperature to 110 ~ 115 DEG C, continues reaction 1 ~ 2h, cooling, filtration, dry, 2-methoxyl group-4-hydroxypropiophenonepreparation can be obtained.
The invention has the beneficial effects as follows: the present invention, not only method is simple, and running cost reduces, and gentleer in reaction process, and yield significantly improves, up to more than 85%.
Embodiment
The building-up process of a kind of 2-methoxyl group-4-hydroxypropiophenonepreparation that the present invention relates to comprises the following steps:
First get 50 ~ 100g phenol and put into reactor, add the CH of 20 ~ 25 DEG C wherein
3i solution, until phenol solution is dissolved completely, adds 4 ~ 10g sodium hydroxide afterwards more wherein, after stirring, uses mixed gas to container sealing simultaneously and is forced into 0.5 ~ 0.8MPa, reacting 1 ~ 1.5h, obtain p-methyl phenol after leaving standstill at 20 ~ 40 DEG C; Then, in the four-hole bottle of upper device agitator, prolong, dropping funnel and thermometer respectively, at normal temperatures, pour above-mentioned obtained p-methyl phenol into, and add the CaO of gained p-methyl phenol quality 0.3 ~ 0.5 times wherein
2with the magnesium oxide of 0.2 ~ 0.4 times, rapidly promote temperature to 30 ~ 35 DEG C, after stirring, fast-sealing container, in 5 ~ 10s by the pressure in container as standard atmospheric pressure, after reaction 30 ~ 45min, obtain p-Hydroxybenzaldehyde; Subsequently in p-Hydroxybenzaldehyde obtained above, adding 100 ~ 150mL mass concentration is immediately the HAC solution of 37% and the bromine liquid of 80 ~ 120mL, 10 ~ 15min is left standstill after stirring, put into stirrer afterwards, arranging rotating speed is 300 ~ 400r/min, and temperature is set to 80 ~ 100 DEG C, when liquid in containers is less than 1/3 of original volume, stop rotating speed and heating, naturally cool to room temperature, 2-bromine p-Hydroxybenzaldehyde can be obtained; After afterwards the 2-bromine p-Hydroxybenzaldehyde obtained being cooled to-3 DEG C, the nitroethane of 100 ~ 120mL is dripped while stirring under negative pressure 1.2 ~ 1.5MPa, rate of addition is 2 ~ 3 per second, after being added dropwise to complete at-3 ~ 2 DEG C stirring reaction 1 ~ 2h, improving temperature is afterwards normal temperature, obtains the bromo-4-hydroxyl of 2-nitro-1-(2-after filtration) phenylallene; Next the bromo-4-hydroxyl of 2-nitro-1-(2-obtained after filtering) phenylallene is positioned over after sterilization again, be equipped with in the four-hole bottle of agitator, prolong, dropping funnel and thermometer, add the Fe of 0.2 ~ 0.5g simultaneously, be heated to 105 DEG C, add with the form dripped the HCl solution that 50 ~ 60mL mass concentration is 40% more afterwards, be added dropwise to complete in 1 ~ 3min, after stirring, sealed reaction 1 ~ 2h, naturally cools to room temperature subsequently, obtains the bromo-4-hydroxypropiophenonepreparation of 2-; Be finally 0.5 ~ 0.6MPa by bromo-for the 2-obtained 4-hydroxypropiophenonepreparation at pressure, temperature is under the condition of 105 ~ 110 DEG C, adds the CH of 30 ~ 35mL
3the PCl of OH solution and 25 ~ 50mL
3solution, and adjust ph is 5.5 ~ 6.5, after being uniformly mixed, and improves temperature to 110 ~ 115 DEG C, continues reaction 1 ~ 2h, cooling, filtration, dry, 2-methoxyl group-4-hydroxypropiophenonepreparation can be obtained.
Example 1
First get 50g phenol and put into reactor, add the CH of 20 DEG C wherein
3i solution, until phenol solution is dissolved completely, adds 4g sodium hydroxide afterwards more wherein, after stirring, uses mixed gas to container sealing simultaneously and is forced into 0.5MPa, reacting 1h, obtain p-methyl phenol after leaving standstill at 20 DEG C; Then, in the four-hole bottle of upper device agitator, prolong, dropping funnel and thermometer respectively, at normal temperatures, pour above-mentioned obtained p-methyl phenol into, and add the CaO of gained p-methyl phenol quality 0.3 times wherein
2with the magnesium oxide of 0.2 times, rapidly promote temperature to 30 DEG C, after stirring, fast-sealing container, in 5s by the pressure in container as standard atmospheric pressure, after reaction 30min, obtain p-Hydroxybenzaldehyde; Subsequently in p-Hydroxybenzaldehyde obtained above, adding 100mL mass concentration is immediately the HAC solution of 37% and the bromine liquid of 80mL, 10min is left standstill after stirring, put into stirrer afterwards, arranging rotating speed is 300r/min, and temperature is set to 80 DEG C, when liquid in containers is less than 1/3 of original volume, stop rotating speed and heating, naturally cool to room temperature, 2-bromine p-Hydroxybenzaldehyde can be obtained; After afterwards the 2-bromine p-Hydroxybenzaldehyde obtained being cooled to-3 DEG C, the nitroethane of 100mL is dripped while stirring under negative pressure 1.2MPa, rate of addition is 2 per second, after being added dropwise to complete at-3 DEG C stirring reaction 1h, improving temperature is afterwards normal temperature, obtains the bromo-4-hydroxyl of 2-nitro-1-(2-after filtration) phenylallene; Next the bromo-4-hydroxyl of 2-nitro-1-(2-obtained after filtering) phenylallene is positioned over after sterilization again, be equipped with in the four-hole bottle of agitator, prolong, dropping funnel and thermometer, add the Fe of 0.2g simultaneously, be heated to 105 DEG C, add with the form dripped the HCl solution that 50mL mass concentration is 40% more afterwards, be added dropwise to complete in 1min, after stirring, sealed reaction 1h, naturally cools to room temperature subsequently, obtains the bromo-4-hydroxypropiophenonepreparation of 2-; Be finally 0.5MPa by bromo-for the 2-obtained 4-hydroxypropiophenonepreparation at pressure, temperature is under the condition of 105 DEG C, adds the CH of 30mL
3the PCl of OH solution and 25mL
3solution, and adjust ph is 5.5, after being uniformly mixed, and improves temperature to 110 DEG C, continues reaction 1h, cooling, filtration, dry, 2-methoxyl group-4-hydroxypropiophenonepreparation can be obtained.
Present method is unique novel, and do not pollute for environment in operation, reaction process is easy, gentle, makes finally to obtain 2-methoxyl group-4-hydroxypropiophenonepreparation 5.2g, and yield reaches 85.8%.
Example 2
First get 80g phenol and put into reactor, add the CH of 23 DEG C wherein
3i solution, until phenol solution is dissolved completely, adds 6g sodium hydroxide afterwards more wherein, after stirring, uses mixed gas to container sealing simultaneously and is forced into 0.6MPa, reacting 1.2h, obtain p-methyl phenol after leaving standstill at 30 DEG C; Then, in the four-hole bottle of upper device agitator, prolong, dropping funnel and thermometer respectively, at normal temperatures, pour above-mentioned obtained p-methyl phenol into, and add the CaO of gained p-methyl phenol quality 0.4 times wherein
2with the magnesium oxide of 0.3 times, rapidly promote temperature to 32 DEG C, after stirring, fast-sealing container, in 8s by the pressure in container as standard atmospheric pressure, after reaction 40min, obtain p-Hydroxybenzaldehyde; Subsequently in p-Hydroxybenzaldehyde obtained above, adding 130mL mass concentration is immediately the HAC solution of 37% and the bromine liquid of 100mL, 13min is left standstill after stirring, put into stirrer afterwards, arranging rotating speed is 350r/min, and temperature is set to 90 DEG C, when liquid in containers is less than 1/3 of original volume, stop rotating speed and heating, naturally cool to room temperature, 2-bromine p-Hydroxybenzaldehyde can be obtained; After afterwards the 2-bromine p-Hydroxybenzaldehyde obtained being cooled to-3 DEG C, the nitroethane of 110mL is dripped while stirring under negative pressure 1.4MPa, rate of addition is 2.5 per second, after being added dropwise to complete at 1 DEG C stirring reaction 1.5h, improving temperature is afterwards normal temperature, obtains the bromo-4-hydroxyl of 2-nitro-1-(2-after filtration) phenylallene; Next the bromo-4-hydroxyl of 2-nitro-1-(2-obtained after filtering) phenylallene is positioned over after sterilization again, be equipped with in the four-hole bottle of agitator, prolong, dropping funnel and thermometer, add the Fe of 0.4g simultaneously, be heated to 105 DEG C, add with the form dripped the HCl solution that 55mL mass concentration is 40% more afterwards, be added dropwise to complete in 2min, after stirring, sealed reaction 1.5h, naturally cools to room temperature subsequently, obtains the bromo-4-hydroxypropiophenonepreparation of 2-; Be finally 0.55MPa by bromo-for the 2-obtained 4-hydroxypropiophenonepreparation at pressure, temperature is under the condition of 107 DEG C, adds the CH of 33mL
3the PCl of OH solution and 40mL
3solution, and adjust ph is 6.2, after being uniformly mixed, and improves temperature to 113 DEG C, continues reaction 1.5h, cooling, filtration, dry, 2-methoxyl group-4-hydroxypropiophenonepreparation can be obtained.
Present method is unique novel, and do not pollute for environment in operation, reaction process is easy, gentle, makes finally to obtain 2-methoxyl group-4-hydroxypropiophenonepreparation 6.5g, and yield reaches 88%.
Example 3
First get 100g phenol and put into reactor, add the CH of 25 DEG C wherein
3i solution, until phenol solution is dissolved completely, adds 10g sodium hydroxide afterwards more wherein, after stirring, uses mixed gas to container sealing simultaneously and is forced into 0.8MPa, reacting 1.5h, obtain p-methyl phenol after leaving standstill at 40 DEG C; Then, in the four-hole bottle of upper device agitator, prolong, dropping funnel and thermometer respectively, at normal temperatures, pour above-mentioned obtained p-methyl phenol into, and add the CaO of gained p-methyl phenol quality 0.5 times wherein
2with the magnesium oxide of 0.4 times, rapidly promote temperature to 35 DEG C, after stirring, fast-sealing container, in 10s by the pressure in container as standard atmospheric pressure, after reaction 45min, obtain p-Hydroxybenzaldehyde; Subsequently in p-Hydroxybenzaldehyde obtained above, adding 150mL mass concentration is immediately the HAC solution of 37% and the bromine liquid of 120mL, 15min is left standstill after stirring, put into stirrer afterwards, arranging rotating speed is 400r/min, and temperature is set to 100 DEG C, when liquid in containers is less than 1/3 of original volume, stop rotating speed and heating, naturally cool to room temperature, 2-bromine p-Hydroxybenzaldehyde can be obtained; After afterwards the 2-bromine p-Hydroxybenzaldehyde obtained being cooled to-3 DEG C, the nitroethane of 120mL is dripped while stirring under negative pressure 1.5MPa, rate of addition is 3 per second, after being added dropwise to complete at 2 DEG C stirring reaction 2h, improving temperature is afterwards normal temperature, obtains the bromo-4-hydroxyl of 2-nitro-1-(2-after filtration) phenylallene; Next the bromo-4-hydroxyl of 2-nitro-1-(2-obtained after filtering) phenylallene is positioned over after sterilization again, be equipped with in the four-hole bottle of agitator, prolong, dropping funnel and thermometer, add the Fe of 0.5g simultaneously, be heated to 105 DEG C, add with the form dripped the HCl solution that 60mL mass concentration is 40% more afterwards, be added dropwise to complete in 3min, after stirring, sealed reaction 2h, naturally cools to room temperature subsequently, obtains the bromo-4-hydroxypropiophenonepreparation of 2-; Be finally 0.6MPa by bromo-for the 2-obtained 4-hydroxypropiophenonepreparation at pressure, temperature is under the condition of 110 DEG C, adds the CH of 35mL
3the PCl of OH solution and 50mL
3solution, and adjust ph is 6.5, after being uniformly mixed, and improves temperature to 115 DEG C, continues reaction 2h, cooling, filtration, dry, 2-methoxyl group-4-hydroxypropiophenonepreparation can be obtained.
Present method is unique novel, and do not pollute for environment in operation, reaction process is easy, gentle, makes finally to obtain 2-methoxyl group-4-hydroxypropiophenonepreparation 7.4g, and yield reaches 90%.
Claims (1)
1. a synthetic method for 2-methoxyl group-4-hydroxypropiophenonepreparation, is characterized in that concrete synthesis step is:
(1) get 50 ~ 100g phenol and put into reactor, add the CH of 20 ~ 25 DEG C wherein
3i solution, until phenol solution is dissolved completely, adds 4 ~ 10g sodium hydroxide afterwards more wherein, after stirring, uses mixed gas to container sealing simultaneously and is forced into 0.5 ~ 0.8MPa, reacting 1 ~ 1.5h, obtain p-methyl phenol after leaving standstill at 20 ~ 40 DEG C;
(2) in the four-hole bottle of upper device agitator, prolong, dropping funnel and thermometer respectively, at normal temperatures, pour above-mentioned obtained p-methyl phenol into, and add the CaO of gained p-methyl phenol quality 0.3 ~ 0.5 times wherein
2with the magnesium oxide of 0.2 ~ 0.4 times, rapidly promote temperature to 30 ~ 35 DEG C, after stirring, fast-sealing container, in 5 ~ 10s by the pressure in container as standard atmospheric pressure, after reaction 30 ~ 45min, obtain p-Hydroxybenzaldehyde;
(3) in p-Hydroxybenzaldehyde obtained above, adding 100 ~ 150mL mass concentration is immediately the HAC solution of 37% and the bromine liquid of 80 ~ 120mL, 10 ~ 15min is left standstill after stirring, put into stirrer afterwards, arranging rotating speed is 300 ~ 400r/min, and temperature is set to 80 ~ 100 DEG C, when liquid in containers is less than 1/3 of original volume, stop rotating speed and heating, naturally cool to room temperature, 2-bromine p-Hydroxybenzaldehyde can be obtained;
(4) after the 2-bromine p-Hydroxybenzaldehyde obtained being cooled to-3 DEG C, the nitroethane of 100 ~ 120mL is dripped while stirring under negative pressure 1.2 ~ 1.5MPa, rate of addition is 2 ~ 3 per second, after being added dropwise to complete at-3 ~ 2 DEG C stirring reaction 1 ~ 2h, improving temperature is afterwards normal temperature, obtains the bromo-4-hydroxyl of 2-nitro-1-(2-after filtration) phenylallene;
(5) the bromo-4-hydroxyl of 2-nitro-1-(2-that obtains after filtering) phenylallene is positioned over after sterilization again, be equipped with in the four-hole bottle of agitator, prolong, dropping funnel and thermometer, add the Fe of 0.2 ~ 0.5g simultaneously, be heated to 105 DEG C, add with the form dripped the HCl solution that 50 ~ 60mL mass concentration is 40% more afterwards, be added dropwise to complete in 1 ~ 3min, after stirring, sealed reaction 1 ~ 2h, naturally cools to room temperature subsequently, obtains the bromo-4-hydroxypropiophenonepreparation of 2-;
(6) be 0.5 ~ 0.6MPa by bromo-for the 2-obtained 4-hydroxypropiophenonepreparation at pressure, temperature is under the condition of 105 ~ 110 DEG C, adds the CH of 30 ~ 35mL
3the PCl of OH solution and 25 ~ 50mL
3solution, and adjust ph is 5.5 ~ 6.5, after being uniformly mixed, and improves temperature to 110 ~ 115 DEG C, continues reaction 1 ~ 2h, cooling, filtration, dry, 2-methoxyl group-4-hydroxypropiophenonepreparation can be obtained.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109809977A (en) * | 2019-01-17 | 2019-05-28 | 江苏理工学院 | A kind of preparation method of the bromo- 4- fluorobenzaldehyde of 2- |
| CN110746281A (en) * | 2019-10-23 | 2020-02-04 | 浙江新和成股份有限公司 | Preparation method of 3-bromo-4-hydroxybenzaldehyde |
| CN115536509A (en) * | 2022-04-06 | 2022-12-30 | 苏州金蚕新材料科技有限公司 | Synthesis method of 2-bromo-4-hydroxybenzaldehyde |
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2015
- 2015-10-31 CN CN201510722070.2A patent/CN105418399A/en active Pending
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| 刘颖等: "4-羟基-3-甲氧基苯基丙酮的合成", 《精细化工中间体》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109809977A (en) * | 2019-01-17 | 2019-05-28 | 江苏理工学院 | A kind of preparation method of the bromo- 4- fluorobenzaldehyde of 2- |
| CN110746281A (en) * | 2019-10-23 | 2020-02-04 | 浙江新和成股份有限公司 | Preparation method of 3-bromo-4-hydroxybenzaldehyde |
| CN110746281B (en) * | 2019-10-23 | 2022-05-03 | 浙江新和成股份有限公司 | Preparation method of 3-bromo-4-hydroxybenzaldehyde |
| CN115536509A (en) * | 2022-04-06 | 2022-12-30 | 苏州金蚕新材料科技有限公司 | Synthesis method of 2-bromo-4-hydroxybenzaldehyde |
| CN115536509B (en) * | 2022-04-06 | 2023-11-07 | 苏州当量生物医药有限公司 | Synthesis method of 2-bromo-4-hydroxybenzaldehyde |
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Application publication date: 20160323 |