CN103508866B - A kind of synthesis technique of salicylic aldehyde - Google Patents
A kind of synthesis technique of salicylic aldehyde Download PDFInfo
- Publication number
- CN103508866B CN103508866B CN201310228080.1A CN201310228080A CN103508866B CN 103508866 B CN103508866 B CN 103508866B CN 201310228080 A CN201310228080 A CN 201310228080A CN 103508866 B CN103508866 B CN 103508866B
- Authority
- CN
- China
- Prior art keywords
- salicylic aldehyde
- magnesium
- toluene
- phenol
- reaction mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A synthesis technique for salicylic aldehyde, the reaction raw materials using phenol, paraformaldehyde etc. cheap and easy to get replaces the noxious solvents such as HMPA, also can not produce toxic substance in reaction.Phenol is in the methanol solution of magnesium methylate, pass through distillating carbinol, generate phenol magnesium, due to the metallic character of magnesium, phenol magnesium is with the reaction process of formaldehyde, and magnesium ion is prior to formaldehyde coordination, formaldehyde after coordination is near the ortho position of phenyl ring, by the parent electricity attack of formaldehyde to phenyl ring ortho position, optionally generate the magnesium salts of salicylic aldehyde, this magnesium salts obtains salicylic aldehyde after dilute hydrochloric acid.This process costs is low, it is little to pollute, harvest rate is high (> 85%), purity high (> 99%), thus has good economic benefit and social benefit.
Description
Technical field
The present invention relates to a kind of organic synthesis intermediate, especially relate to a kind of synthesis technique of salicylic aldehyde.
Background technology
Salicylic aldehyde (Salicylaldehyde) formal name used at school salicylaldhyde, is colourless or weak yellow liquid, has a wide range of applications in medicine, agricultural chemicals, spices, plating, petrochemical industry.In recent years, medicine and perfume industry increasing to the demand without chloro-salicylic aldehyde, make the research and development of the novel process of salicylic aldehyde become one of active field.
The most direct and the synthetic route of salicylic aldehyde introduces a formyl group, and traditional process for hydroformylation, as Reimer ~ Tiemman, being most widely used of Ortho Cresol method.But traditional method for making harvest rate very low (less than 60%) of salicylic aldehyde, causes the production cost of enterprise to remain high.And can the noxious solvents such as HMPA be used in production process, also containing toxic substance in reaction product, therefore there is environmental pollution hidden danger.
Summary of the invention
The object of this invention is to provide a kind of synthesis technique of salicylic aldehyde, to solve, existing salicylic aldehyde production technique harvest rate is low, production cost is high, uses the technical problems such as noxious solvent, environmental pollution are large.
The present invention is mainly solved the problems of the technologies described above by following technical proposals: a kind of synthesis technique of salicylic aldehyde, comprises the following steps:
A. 4A molecular sieve is placed on inside retort furnace and dewaters 5 hours in 400 DEG C of activation, be placed in moisture eliminator and be cooled to room temperature; Get 0.005 ~ 0.006 part of 4A molecular sieve to mix with methyl alcohol 0.5 ~ 0.6 part, by MAGNESIUM METAL 0.1 part, iodine 0.01 part of input reactor, temperature is controlled at 40 DEG C, after being stirred to magnesium completely dissolve, obtain the mixing solutions containing magnesium methylate and methyl alcohol;
B. in reactor, phenol 0.2 ~ 0.3 part is added, polyvinyl alcohol 0.01 ~ 0.03 part, N-acyl group ED3A0.001 ~ 0.02 part, continue stir and be heated to 64 ~ 66 DEG C, treat that most of methyl alcohol distillates, 0.9 ~ 0.98 part of toluene is added in reactor, proceed the distillation also constantly stirring that heats up, distill out the azeotrope of toluene and methyl alcohol, when the temperature of reaction mixture rises to 95 DEG C, 0.7 ~ 0.8 part of paraformaldehyde and 0.3 ~ 0.4 part of toluene is added slowly in reaction mixture, 95 DEG C are kept to react 15 ~ 20 minutes, be cooled to 22 ~ 26 DEG C gradually, filter, get filtrate,
C. in filtrate, 5 ~ 6 part of 10% dilute hydrochloric acid is added, drip 0.5 ~ 0.6 part of volume solubility is the tetramethylammonium hydroxide of 25% simultaneously, reactor is heated to 30 ~ 40 DEG C, and constantly stir 20 ~ 25 minutes, question response mixture cooling leave standstill to 22 DEG C, to be separated go out flaxen oil reservoir and colourless water layer;
D. reaction mixture is sent in swirler, oily water separation is carried out to reaction mixture, to isolated water layer material toluene 1.5 parts of extracting twice, extract and oil reservoir are merged and obtains salicylic aldehyde crude product; In salicylic aldehyde crude product, pass into deionized water 1.67 parts wash, then by oil reservoir material in 195 ~ 198 DEG C, distill under 133.3Pa, gained cut is salicylic aldehyde.
As preferably, described swirler comprises tank body, and tank body top is cylindrical section, and be conical section below cylindrical section, cylindrical section is provided with feed-pipe, and be water outlet bottom conical section, tank body center is provided with reverse stream pipe, and reverse stream pipe top is provided with oil outlet.
4A molecular sieve is a kind of alkali metal aluminosilicate, water a small amount of in energy absorption reaction system.Because the effective pore radius of 4A molecular sieve is 0.4nm, therefore be called 4A molecular sieve.Tetramethylammonium hydroxide (CH3) 4NOH has strong basicity, is easy to remove after catalysis, does not stay any residue.
The reaction raw materials that the present invention uses phenol, paraformaldehyde etc. cheap and easy to get, does not use noxious solvent, also can not produce toxic substance in reaction.Phenol is in the methanol solution of magnesium methylate, pass through distillating carbinol, generate phenol magnesium, due to the metallic character of magnesium, phenol magnesium is with the reaction process of formaldehyde, and magnesium ion is prior to formaldehyde coordination, formaldehyde after coordination is near the ortho position of phenyl ring, by the parent electricity attack of formaldehyde to phenyl ring ortho position, optionally generate the magnesium salts of salicylic aldehyde, this magnesium salts obtains salicylic aldehyde after dilute hydrochloric acid.This process costs is low, it is little to pollute, harvest rate is high (> 85%), purity high (> 99%), thus has good economic benefit and social benefit.
Accompanying drawing explanation
Fig. 1 is the structural representation of swirler.
Embodiment
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Fig. 1 is the structural representation of swirler, and swirler comprises tank body 1, and tank body top is cylindrical section 11, be conical section 12 below cylindrical section 11, cylindrical section 11 is provided with feed-pipe 2, is water outlet 3 bottom conical section 12, tank body 1 center is provided with reverse stream pipe 13, and reverse stream pipe 13 top is provided with oil outlet 4.
Embodiment 1: the synthesis technique of this salicylic aldehyde, comprises the following steps:
A. 4A molecular sieve is placed on inside retort furnace and dewaters 5 hours in 400 DEG C of activation, be placed in moisture eliminator and be cooled to room temperature; Get 0.005 part of (100 grams every part, lower same) 4A molecular sieve to mix with methyl alcohol 0.5 part, by MAGNESIUM METAL 0.1 part, iodine 0.01 part of input reactor, temperature is controlled at 40 DEG C, after being stirred to magnesium completely dissolve, obtain the mixing solutions containing magnesium methylate and methyl alcohol;
B. in reactor, add phenol 0.2 part, polyvinyl alcohol 0.01 part, N-acyl group ED3A0.001 part, continue stir and be heated to 64 DEG C, treat that most of methyl alcohol distillates, 0.9 part of toluene is added in reactor, proceed the distillation also constantly stirring that heats up, distill out the azeotrope of toluene and methyl alcohol, when the temperature of reaction mixture rises to 95 DEG C, 0.7 part of paraformaldehyde and 0.3 part of toluene is added slowly in reaction mixture, 95 DEG C are kept to react 15 minutes, be cooled to 22 DEG C gradually, filter, get filtrate;
C. in filtrate, 5 part of 10% dilute hydrochloric acid is added, drip 0.5 part of volume solubility is the tetramethylammonium hydroxide of 25% simultaneously, reactor is heated to 40 DEG C, and constantly stirs 20 minutes, question response mixture cooling leave standstill to 22 DEG C, to be separated go out flaxen oil reservoir and colourless water layer;
D. reaction mixture is sent in swirler, oily water separation is carried out to reaction mixture, to isolated water layer material toluene 1.5 parts of extracting twice, extract and oil reservoir are merged and obtains salicylic aldehyde crude product; In salicylic aldehyde crude product, pass into deionized water 1.67 parts wash, then by oil reservoir material in 195 DEG C, distill under 133.3Pa, gained cut is salicylic aldehyde.
Use nucleus magnetic hydrogen spectrum analyser to detect product, recording the clean yield of salicylic aldehyde is 86%.
Embodiment 2: the synthesis technique of this salicylic aldehyde, comprises the following steps:
A. 4A molecular sieve is placed on inside retort furnace and dewaters 5 hours in 400 DEG C of activation, be placed in moisture eliminator and be cooled to room temperature; Get 0.0055 part of 4A molecular sieve to mix with methyl alcohol 0.55 part, by MAGNESIUM METAL 0.1 part, iodine 0.01 part of input reactor, temperature is controlled at 40 DEG C, after being stirred to magnesium completely dissolve, obtain the mixing solutions containing magnesium methylate and methyl alcohol;
B. in reactor, add phenol 0.25 part, polyvinyl alcohol 0.02 part, N-acyl group ED3A0.01 part, continue stir and be heated to 65 DEG C, treat that most of methyl alcohol distillates, 0.94 part of toluene is added in reactor, proceed the distillation also constantly stirring that heats up, distill out the azeotrope of toluene and methyl alcohol, when the temperature of reaction mixture rises to 95 DEG C, 0.75 part of paraformaldehyde and 0.35 part of toluene is added slowly in reaction mixture, 95 DEG C are kept to react 17 minutes, be cooled to 24 DEG C gradually, filter, get filtrate;
C. in filtrate, 5.5 part of 10% dilute hydrochloric acid is added, drip 0.55 part of volume solubility is the tetramethylammonium hydroxide of 25% simultaneously, reactor is heated to 35 DEG C, and constantly stirs 22 minutes, question response mixture cooling leave standstill to 22 DEG C, to be separated go out flaxen oil reservoir and colourless water layer;
D. reaction mixture is sent in swirler, oily water separation is carried out to reaction mixture, to isolated water layer material toluene 1.5 parts of extracting twice, extract and oil reservoir are merged and obtains salicylic aldehyde crude product; In salicylic aldehyde crude product, pass into deionized water 1.67 parts wash, then by oil reservoir material in 196 DEG C, distill under 133.3Pa, gained cut is salicylic aldehyde.
Use nucleus magnetic hydrogen spectrum analyser to detect product, recording the clean yield of salicylic aldehyde is 87%.
Embodiment 3: the synthesis technique of this salicylic aldehyde, comprises the following steps:
A. 4A molecular sieve is placed on inside retort furnace and dewaters 5 hours in 400 DEG C of activation, be placed in moisture eliminator and be cooled to room temperature; Get 0.006 part of 4A molecular sieve to mix with methyl alcohol 0.6 part, by MAGNESIUM METAL 0.1 part, iodine 0.01 part of input reactor, temperature is controlled at 40 DEG C, after being stirred to magnesium completely dissolve, obtain the mixing solutions containing magnesium methylate and methyl alcohol;
B. in reactor, add phenol 0.3 part, polyvinyl alcohol 0.03 part, N-acyl group ED3A0.02 part, continue stir and be heated to 66 DEG C, treat that most of methyl alcohol distillates, 0.98 part of toluene is added in reactor, proceed the distillation also constantly stirring that heats up, distill out the azeotrope of toluene and methyl alcohol, when the temperature of reaction mixture rises to 95 DEG C, 0.8 part of paraformaldehyde and 0.4 part of toluene is added slowly in reaction mixture, 95 DEG C are kept to react 20 minutes, be cooled to 26 DEG C gradually, filter, get filtrate;
C. in filtrate, 6 part of 10% dilute hydrochloric acid is added, drip 0.6 part of volume solubility is the tetramethylammonium hydroxide of 25% simultaneously, reactor is heated to 30 DEG C, and constantly stirs 25 minutes, question response mixture cooling leave standstill to 22 DEG C, to be separated go out flaxen oil reservoir and colourless water layer;
D. reaction mixture is sent in swirler, oily water separation is carried out to reaction mixture, to isolated water layer material toluene 1.5 parts of extracting twice, extract and oil reservoir are merged and obtains salicylic aldehyde crude product; In salicylic aldehyde crude product, pass into deionized water 1.67 parts wash, then by oil reservoir material in 198 DEG C, distill under 133.3Pa, gained cut is salicylic aldehyde.
Use nucleus magnetic hydrogen spectrum analyser to detect product, recording the clean yield of salicylic aldehyde is 89%.
The salicylic aldehyde that embodiment 1-3 is obtained and contrasting by salicylic aldehyde prepared by existing method, comparing result is as following table:
| Distinguish | Harvest rate | Salicylic aldehyde purity | Phenol content | Other component contents |
| Embodiment 1 | 86% | 99.5% | 0.4% | 0.1% |
| Embodiment 2 | 87% | 99.6% | 0.3% | 0.1% |
| Embodiment 3 | 89% | 99.6% | 0.3% | 0.1% |
| Currently available products | 72% | 95.2% | 1.9% | 2.9% |
Known by above Data Comparison, its harvest rate of the salicylic aldehyde adopting technique of the present invention to produce, purity are all better than commercially available prod.
Claims (1)
1. a synthesis technique for salicylic aldehyde, is characterized in that this technique comprises the following steps:
A. 4A molecular sieve is placed on inside retort furnace and dewaters 5 hours in 400 DEG C of activation, be placed in moisture eliminator and be cooled to room temperature; Get 0.005 ~ 0.006 part of 4A molecular sieve to mix with methyl alcohol 0.5 ~ 0.6 part, by MAGNESIUM METAL 0.1 part, iodine 0.01 part of input reactor, temperature is controlled at 40 DEG C, after being stirred to magnesium completely dissolve, obtain the mixing solutions containing magnesium methylate and methyl alcohol;
B. in reactor, phenol 0.2 ~ 0.3 part is added, polyvinyl alcohol 0.01 ~ 0.03 part, N-acyl group ED3A0.001 ~ 0.02 part, continue stir and be heated to 64 ~ 66 DEG C, treat that most of methyl alcohol distillates, 0.9 ~ 0.98 part of toluene is added in reactor, proceed the distillation also constantly stirring that heats up, distill out the azeotrope of toluene and methyl alcohol, when the temperature of reaction mixture rises to 95 DEG C, 0.7 ~ 0.8 part of paraformaldehyde and 0.3 ~ 0.4 part of toluene is added slowly in reaction mixture, 95 DEG C are kept to react 15 ~ 20 minutes, be cooled to 22 ~ 26 DEG C gradually, filter, get filtrate,
C. in filtrate, 5 ~ 6 part of 10% dilute hydrochloric acid is added, drip 0.5 ~ 0.6 part of volume solubility is the tetramethylammonium hydroxide of 25% simultaneously, reactor is heated to 30 ~ 40 DEG C, and constantly stir 20 ~ 25 minutes, question response mixture cooling leave standstill to 22 DEG C, to be separated go out flaxen oil reservoir and colourless water layer;
D. reaction mixture is sent in swirler, oily water separation is carried out to reaction mixture, to isolated water layer material toluene 1.5 parts of extracting twice, extract and oil reservoir are merged and obtains salicylic aldehyde crude product; In salicylic aldehyde crude product, pass into deionized water 1.67 parts wash, then by oil reservoir material in 195 ~ 198 DEG C, distill under 133.3Pa, gained cut is salicylic aldehyde;
Described swirler comprises tank body, and tank body top is cylindrical section, and be conical section below cylindrical section, cylindrical section is provided with feed-pipe, and be water outlet bottom conical section, tank body center is provided with reverse stream pipe, and reverse stream pipe top is provided with oil outlet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310228080.1A CN103508866B (en) | 2013-06-09 | 2013-06-09 | A kind of synthesis technique of salicylic aldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310228080.1A CN103508866B (en) | 2013-06-09 | 2013-06-09 | A kind of synthesis technique of salicylic aldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103508866A CN103508866A (en) | 2014-01-15 |
| CN103508866B true CN103508866B (en) | 2015-09-09 |
Family
ID=49892354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310228080.1A Active CN103508866B (en) | 2013-06-09 | 2013-06-09 | A kind of synthesis technique of salicylic aldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103508866B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669414A (en) * | 2015-12-09 | 2016-06-15 | 南通江天化学股份有限公司 | Preparation method for salicylaldehyde |
| CN108500852A (en) * | 2018-05-31 | 2018-09-07 | 富士和机械工业（湖北）有限公司 | A kind of precision casting sanding system |
| CN117164444B (en) * | 2023-09-01 | 2024-07-02 | 浙江宏达化学制品有限公司 | Synthesis method of salicylaldehyde |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5841834A (en) * | 1981-09-07 | 1983-03-11 | Sumitomo Chem Co Ltd | Preparation of hydroxybenzaldehyde |
| CN101161620A (en) * | 2007-11-23 | 2008-04-16 | 南京青石科技发展有限公司 | Method for preparing iodo salicylaldehyde |
| CN101531577B (en) * | 2009-04-08 | 2012-05-23 | 江苏食品职业技术学院 | A method for preparing 3, 4-dihydroxy benzaldehyde in ionic liquid with one-pot method |
-
2013
- 2013-06-09 CN CN201310228080.1A patent/CN103508866B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103508866A (en) | 2014-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cheng et al. | Applications of deep eutectic solvents for hard-to-separate liquid systems | |
| Yi et al. | Visible-light-induced acetalization of aldehydes with alcohols | |
| CN105237371B (en) | Method for preparing vanillin by catalytic oxidative degradation of lignin | |
| Li et al. | Extraction of acetic acid, glycolaldehyde and acetol from aqueous solutions mimicking pyrolysis oil cuts using ionic liquids | |
| CN107159270B (en) | A kind of magnetism hydrogenation deoxidation catalyst and its preparation method and application | |
| CN103508866B (en) | A kind of synthesis technique of salicylic aldehyde | |
| CN105061385B (en) | A kind of method that alkali ionic liquid catalyzes and synthesizes 4H benzos [b] pyran derivate | |
| Ji et al. | Removal of the neutral oil entrained in deep eutectic solvents using an anti-extraction method | |
| Zhu et al. | An efficient and recyclable catalytic system comprising nanopalladium (0) and a pyridinium salt of iron bis (dicarbollide) for oxidation of substituted benzyl alcohol and lignin | |
| CN103215058A (en) | Method for extracting and separating light component from coal tar at low temperature | |
| CN104324519A (en) | Method for directly separating phenols from coal pyrolytic oil | |
| CN104788271A (en) | Synthetic method for preparing alpha, beta-unsaturated ketone | |
| JP6395812B2 (en) | Method for depolymerizing lignin | |
| Firouzabadi et al. | H3PW12O40 as a useful recyclable heterogeneous catalyst for the facile and highly efficient michael addition reaction of thiols to α, β-unsaturated ketones | |
| Hu et al. | Metal‐and Solvent‐Free Transesterification and Aldol Condensation Reactions by a Homogenous Recyclable Basic Ionic Liquid Based on the 1, 3, 5‐Triazine Framework | |
| US8952201B2 (en) | Separation method of acetophenone and A-methylbenzyl alcohol | |
| CN102633768B (en) | Method for transforming cisconfiguration of oxane compounds to transconfiguration | |
| CN103880603A (en) | Method for preparing styrenated phenol by catalysis | |
| CN104355982B (en) | A kind of method being prepared oxyacetic acid by glycerine | |
| Khaligh et al. | Saccharin: a cheap and mild acidic agent for the synthesis of azo dyes via telescoped dediazotization | |
| CN113185388B (en) | Method for selectively extracting monophenol from biological oil | |
| CN106316767B (en) | Lactone compound aromatization method | |
| CN102863322A (en) | Method for synthesizing p-methoxylbenzaldehyde | |
| CN102816048A (en) | Method for extracting and separating 1,3-propanediol from fermentation liquid | |
| CN105439994A (en) | Method for preparing furfural from corncobs through microwave assisted SnCl4 catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: What village 433000 Chong town mayor Xiantao in Hubei Province Patentee after: Hubei Sheng Sheng Polytron Technologies Inc Address before: What village 433000 Chong town mayor Xiantao in Hubei Province Patentee before: Hubei Xiansheng Technology Co., Ltd. |