CN104447304A - Preparation method of carboxybenzaldehyde - Google Patents
Preparation method of carboxybenzaldehyde Download PDFInfo
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- CN104447304A CN104447304A CN201410698640.4A CN201410698640A CN104447304A CN 104447304 A CN104447304 A CN 104447304A CN 201410698640 A CN201410698640 A CN 201410698640A CN 104447304 A CN104447304 A CN 104447304A
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- carboxybenzaldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of carboxybenzaldehyde. The preparation method comprises the following steps: (1) adding carbon tetrachloride and phthalide in a reaction kettle, performing heating and pressurization, inletting chlorine, continuing heating and warming, and performing a reflux reaction; (2) inletting carbon dioxide in the reaction kettle, performing decompressing and drying by distillation, and performing cooling and drying so as to obtain 3-chlorophthalide; (3) adding deionized water into a hydrolysis kettle, performing heating and warming, adding the 3-chlorophthalide, performing water bath heating, performing cooling, precipitating crystals, performing suction filtration and obtaining a wet product of the carboxybenzaldehyde; (4) performing recrystallization on the wet product of the carboxybenzaldehyde and obtaining the carboxybenzaldehyde. The preparation method disclosed by the invention has the advantages of simple steps and convenient operation, and the yield coefficient and the purity of the prepared carboxybenzaldehyde are high.
Description
Technical field
The present invention relates to medicine intermediate technical field, particularly relate to a kind of preparation method of 2-carboxybenzaldehyde.
Background technology
2-carboxybenzaldehyde is a kind of important intermediate of synthesis antipyretic and analgesic, and No. CAS is 119-67-52, and be a kind of white to off-white color crystalline powder, fusing point is 96 ~ 100 DEG C.
In prior art, 2-carboxybenzaldehyde by phenol through bromination, hydrolysis and obtaining.Heated by phenol, logical bromine reaction, control to pass into speed, the essentially no bromine vapor of reaction end gas is discharged, and logical bromine is finished, and reactant adds water, and is hydrolyzed.Cooling, separates out 2-carboxybenzaldehyde.This preparation method's complex steps, controllability are poor, and the 2-carboxybenzaldehyde yield of preparation is low, purity is low.
Summary of the invention
In view of this, the invention provides a kind of preparation method of 2-carboxybenzaldehyde, this preparation method's step is simple, easy to operate, and obtained 2-carboxybenzaldehyde yield is high, purity is high.
A preparation method for 2-carboxybenzaldehyde, comprises the following steps:
(1) tetracol phenixin, phthalide are added in reactor, heating and pressurizing, after passing into chlorine, continue heat temperature raising, carry out back flow reaction;
(2) in reactor, pass into carbonic acid gas and evaporated under reduced pressure, cooling, after drying, obtains 3-chlorobenzene phthalein;
(3) join in hydrolysis kettle by deionized water, drop into 3-chlorobenzene phthalein, carry out heating in water bath after heat temperature raising, cooling, crystallization, suction filtration obtains 2-carboxybenzaldehyde wet product;
(4) 2-carboxybenzaldehyde wet product is carried out recrystallization, obtained 2-carboxybenzaldehyde.
The present invention adopts tetracol phenixin as organic solvent, and chlorine oxidation is good, and with phthalide sufficient reacting, and chlorine and phthalide are all soluble in tetracol phenixin, and chlorination reaction can be made more abundant, and the amount passing into chlorine is easily controlled, and preparation process is simple, easy to operate.
Preferably, step (1) detailed process is: by mass parts, 80 ~ 160 parts, tetracol phenixin, phthalide 130 ~ 150 parts are added in reactor, be heated to 105 ~ 110 DEG C, be forced into 8 ~ 10Mpa, pass into chlorine 80 ~ 150 parts of post-heating to 115 ~ 120 DEG C, carry out back flow reaction 1 ~ 1.5h.
Preferably, step (2) detailed process is: at 120 ~ 130 DEG C of temperature, pass into carbonic acid gas 1.5 ~ 2h, and evaporated under reduced pressure removes residual impurity in reactor, is cooled to 8 ~ 10 DEG C, at 18 ~ 25 DEG C, carry out drying, obtains 3-chlorobenzene phthalein.
Preferably, in step (3), water bath heating temperature is 95 ~ 100 DEG C.
Preferably, the detailed process of step (3) is: join in hydrolysis kettle by deionized water 30 ~ 80 parts, be heated to 90 ~ 95 DEG C, drop into described 3-chlorobenzene phthalein, carry out 100 DEG C of heating in water bath 2h, be cooled to 8 ~ 10 DEG C, crystallization, suction filtration obtains 2-carboxybenzaldehyde wet product.
Preferably, in step (4), drying temperature is 15 ~ 20 DEG C, and time of drying is 2 ~ 3h.
Preferably, step (4) detailed process is: join in deionized water by 2-carboxybenzaldehyde wet product, adds gac and carries out suction filtration, be cooled to 0 ~ 5 DEG C, crystallization, carry out drying, obtain 2-carboxybenzaldehyde at 18 DEG C.
Beneficial effect of the present invention: a kind of preparation method of 2-carboxybenzaldehyde comprises the following steps: tetracol phenixin, phthalide add in reactor by (1), heating and pressurizing continues heat temperature raising after passing into chlorine, carries out back flow reaction; (2) in reactor, pass into carbonic acid gas and evaporated under reduced pressure, cooling, after drying, obtains 3-chlorobenzene phthalein; (3) join in hydrolysis kettle by deionized water, drop into 3-chlorobenzene phthalein, carry out heating in water bath after heat temperature raising, cooling, crystallization, suction filtration obtains 2-carboxybenzaldehyde wet product; (4) 2-carboxybenzaldehyde wet product is carried out recrystallization, obtained 2-carboxybenzaldehyde.Preparation method's step of the present invention is simple, easy to operate, and obtained 2-carboxybenzaldehyde yield is high, purity is high.
Embodiment
Further illustrate technical scheme of the present invention respectively below in conjunction with the embodiments.
Raw material involved in following examples is commercially available.
Embodiment 1: the preparation method of a kind of 2-carboxybenzaldehyde of the present embodiment, comprises the following steps:
By mass parts, 80 parts, tetracol phenixin, phthalide 130 parts are added in reactor, is heated to 105 DEG C, is forced into 8Mpa, pass into chlorine 80 parts of post-heating to 115 DEG C, carry out back flow reaction 1h, be heated to 120 DEG C of temperature, in reactor, pass into carbonic acid gas 1.5h, and evaporated under reduced pressure removes residual impurity, be cooled to 8 DEG C, at 18 DEG C, carry out drying, obtain 3-chlorobenzene phthalein;
Deionized water 30 parts is joined in hydrolysis kettle, is heated to 90 DEG C, drop into the 3-chlorobenzene phthalein obtained, carry out 100 DEG C of heating in water bath 2h, be cooled to 8 DEG C, crystallization, suction filtration obtains 2-carboxybenzaldehyde wet product, 2-carboxybenzaldehyde wet product is joined in deionized water, add gac and carry out suction filtration, be cooled to 0 DEG C, crystallization, at 15 DEG C, carry out dry 2h, obtain 2-carboxybenzaldehyde.
Embodiment 2: the preparation method of a kind of 2-carboxybenzaldehyde of the present embodiment, comprises the following steps:
By mass parts, 100 parts, tetracol phenixin, phthalide 140 parts are added in reactor, is heated to 110 DEG C, is forced into 9Mpa, pass into chlorine 120 parts of post-heating to 120 DEG C, carry out back flow reaction 1.5h, at 120 DEG C of temperature, in reactor, pass into carbonic acid gas 2h, and evaporated under reduced pressure removes residual impurity, be cooled to 10 DEG C, at 20 DEG C, carry out drying, obtain 3-chlorobenzene phthalein;
Deionized water 60 parts is joined in hydrolysis kettle, is heated to 90 DEG C, drop into obtained 3-chlorobenzene phthalein, carry out 100 DEG C of heating in water bath 2h, be cooled to 10 DEG C, crystallization, suction filtration obtains 2-carboxybenzaldehyde wet product, 2-carboxybenzaldehyde wet product is joined in deionized water, add gac and carry out suction filtration, be cooled to 2 DEG C, crystallization, at 18 DEG C, carry out dry 2.5h, obtain 2-carboxybenzaldehyde.
Embodiment 3: the preparation method of a kind of 2-carboxybenzaldehyde of the present embodiment, comprises the following steps:
By mass parts, 160 parts, tetracol phenixin, phthalide 150 parts are added in reactor, is heated to 110 DEG C, is forced into 10Mpa, pass into chlorine 150 parts of post-heating to 120 DEG C, carry out back flow reaction 1.5h, at 130 DEG C of temperature, in reactor, pass into carbonic acid gas 2h, and evaporated under reduced pressure removes residual impurity, be cooled to 10 DEG C, at 25 DEG C, carry out drying, obtain 3-chlorobenzene phthalein;
Deionized water 80 parts is joined in hydrolysis kettle, is heated to 95 DEG C, drop into described 3-chlorobenzene phthalein, carry out 100 DEG C of heating in water bath 2h, be cooled to 10 DEG C, crystallization, suction filtration obtains 2-carboxybenzaldehyde wet product, 2-carboxybenzaldehyde wet product is joined in deionized water, add gac and carry out suction filtration, be cooled to 5 DEG C, crystallization, at 20 DEG C, carry out dry 3h, obtain 2-carboxybenzaldehyde.
Embodiment 1 ~ 3 is obtained 2-carboxybenzaldehyde and adopt the obtained 2-carboxybenzaldehyde of background technology to carry out purity and yield compares, result is as following table:
As can be seen from the table the 2-carboxybenzaldehyde purity prepared of the present invention and yield high.
The present invention adopts tetracol phenixin as organic solvent, and chlorine oxidation is good, and with phthalide sufficient reacting, and chlorine and phthalide are all soluble in tetracol phenixin, and chlorination reaction can be made more abundant, and the amount passing into chlorine is easily controlled, and preparation process is simple, easy to operate.
Preparation method's step of the present invention is simple, easy to operate, and obtained 2-carboxybenzaldehyde yield is high, purity is high.
It should be noted that and understand, when not departing from the spirit and scope of accompanying claim the present invention for required protection, various amendment and improvement can be made to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not by the restriction of given any specific exemplary teachings.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (8)
1. a preparation method for 2-carboxybenzaldehyde, is characterized in that, comprises the following steps:
(1) tetracol phenixin, phthalide are added in reactor, heating and pressurizing, after passing into chlorine, continue heat temperature raising, carry out back flow reaction;
(2) in reactor, pass into carbonic acid gas and evaporated under reduced pressure, cooling, after drying, obtains 3-chlorobenzene phthalein;
(3) join in hydrolysis kettle by deionized water, drop into 3-chlorobenzene phthalein, carry out heating in water bath after heat temperature raising, cooling, crystallization, suction filtration obtains 2-carboxybenzaldehyde wet product;
(4) 2-carboxybenzaldehyde wet product is carried out recrystallization, obtained 2-carboxybenzaldehyde.
2. preparation method according to claim 1, is characterized in that, in step (1), Heating temperature is 105 ~ 110 DEG C, and moulding pressure is 8 ~ 10Mpa.
3. preparation method according to claim 1, it is characterized in that, step (1) detailed process is: by mass parts, 80 ~ 160 parts, tetracol phenixin, phthalide 130 ~ 150 parts are added in reactor, heating and pressurizing, pass into chlorine 80 ~ 150 parts of post-heating to 115 ~ 120 DEG C, carry out back flow reaction 1 ~ 1.5h.
4. preparation method according to claim 1, it is characterized in that, step (2) detailed process is: at 120 ~ 130 DEG C of temperature, carbonic acid gas 1.5 ~ 2h is passed in reactor, and evaporated under reduced pressure removes residual impurity, be cooled to 8 ~ 10 DEG C, at 18 ~ 25 DEG C, carry out drying, obtain 3-chlorobenzene phthalein.
5. preparation method according to claim 1, is characterized in that, in step (3), water bath heating temperature is 95 ~ 100 DEG C.
6. preparation method according to claim 1, it is characterized in that, the detailed process of step (3) is: join in hydrolysis kettle by deionized water 30 ~ 80 parts, be heated to 90 ~ 95 DEG C, drop into described 3-chlorobenzene phthalein, carry out 100 DEG C of heating in water bath 2h, be cooled to 8 ~ 10 DEG C, crystallization, suction filtration obtains 2-carboxybenzaldehyde wet product.
7. preparation method according to claim 1, is characterized in that, in step (4), drying temperature is 15 ~ 20 DEG C, and time of drying is 2 ~ 3h.
8. preparation method according to claim 1, it is characterized in that, step (4) detailed process is: join in deionized water by 2-carboxybenzaldehyde wet product, add gac and carry out suction filtration, be cooled to 0 ~ 5 DEG C, crystallization, carries out drying, obtains 2-carboxybenzaldehyde at 18 DEG C.
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| CN201410698640.4A CN104447304A (en) | 2014-11-26 | 2014-11-26 | Preparation method of carboxybenzaldehyde |
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| CN201410698640.4A CN104447304A (en) | 2014-11-26 | 2014-11-26 | Preparation method of carboxybenzaldehyde |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115385787A (en) * | 2022-10-28 | 2022-11-25 | 寿光祥铭化工有限公司 | Preparation method of 2-carboxyl benzaldehyde |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2805990A1 (en) * | 1978-02-13 | 1979-08-16 | Dynamit Nobel Ag | Phthalaldehyde acid prodn. from 3-chloro-phthalide - by hydrolysis in recycled mother liquor, useful as pharmaceutical intermediates |
| JPH0827060A (en) * | 1994-07-22 | 1996-01-30 | Nippon Light Metal Co Ltd | Production of high-purity orthoformylbenzoic acid |
| CN101735041A (en) * | 2009-12-17 | 2010-06-16 | 太仓市运通化工厂 | Preparation method of 2-carboxybenzaldehyde |
-
2014
- 2014-11-26 CN CN201410698640.4A patent/CN104447304A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2805990A1 (en) * | 1978-02-13 | 1979-08-16 | Dynamit Nobel Ag | Phthalaldehyde acid prodn. from 3-chloro-phthalide - by hydrolysis in recycled mother liquor, useful as pharmaceutical intermediates |
| JPH0827060A (en) * | 1994-07-22 | 1996-01-30 | Nippon Light Metal Co Ltd | Production of high-purity orthoformylbenzoic acid |
| CN101735041A (en) * | 2009-12-17 | 2010-06-16 | 太仓市运通化工厂 | Preparation method of 2-carboxybenzaldehyde |
Non-Patent Citations (3)
| Title |
|---|
| DESAI, R. A.等: "Preparation of N-[-(4-aryl-1-piperazinyl)ethyl/propyl]-3-hydroxyphthalimidines", 《INDIAN JOURNAL OF CHEMISTRY》 * |
| 张跃 主编: "《精细化工中间体生产流程图解》", 31 May 1999, 化学工业出版社 * |
| 李果 等: "3 位取代苯酞衍生物新的简便合成方法", 《精细与专用化学品》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115385787A (en) * | 2022-10-28 | 2022-11-25 | 寿光祥铭化工有限公司 | Preparation method of 2-carboxyl benzaldehyde |
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Application publication date: 20150325 |