CN117700312B - Synthesis method of 2, 2-dimethoxy acetaldehyde - Google Patents
Synthesis method of 2, 2-dimethoxy acetaldehydeInfo
- Publication number
- CN117700312B CN117700312B CN202311545596.9A CN202311545596A CN117700312B CN 117700312 B CN117700312 B CN 117700312B CN 202311545596 A CN202311545596 A CN 202311545596A CN 117700312 B CN117700312 B CN 117700312B
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- glyoxal
- methanol
- dimethoxyacetaldehyde
- dehydrated
- film evaporator
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 2, 2-dimethoxy acetaldehyde, which comprises the steps of firstly adopting a thin film evaporator to dehydrate industrial 40% glyoxal aqueous solution, then taking N-sulfonic acid saccharin as a catalyst, and reacting with methanol at a certain temperature to prepare 2, 2-dimethoxy acetaldehyde reaction liquid. The invention does not need to add extra reagent, the reaction period is short, and the product yield can reach more than 70%.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a synthesis method of 2, 2-dimethoxy acetaldehyde.
Background
2, 2-Dimethoxy aldehyde is colorless, low-toxicity and non-volatile aldehyde, contains an aldehyde group with higher reactivity and an acetal group with lower reactivity but can be easily converted into the aldehyde group, is commonly applied to the reactions of closing a ring, prolonging a parent chain structure, introducing the aldehyde group and the like in synthetic chemistry, and is widely applied to the resin industry, the perfume industry, the medicine industry and the like as an important fine intermediate.
The synthesis of 2, 2-dimethoxy acetaldehyde is mainly prepared by taking glyoxal and methanol as raw materials and carrying out acid catalytic dehydration under certain conditions, as in patent (CN 103242145A), patent (CN 1l 84801A) reports that glyoxal, glyoxal diacetal and methanol are adopted to react under the catalysis of an acid resin to prepare 2, 2-dimethoxy acetaldehyde, patent (CN)
101676252A) the preparation of 2, 2-dimethoxyacetaldehyde by reacting glyoxal, the corresponding ester of methanol and methanol under catalysis of an acidic resin, and CHASTRETTE et al in (The Monoacetalization of Glyoxal:A Direct of 2,2-dimethoxy and Diethoxy Ethanals,Synthetic Communication,1988,18(2),1343-1348) describe acetalization of glyoxal in the presence of chloroform, an azeotropic agent, using a Soxhlett apparatus filled with a drying agent to remove water produced during the preparation. However, these methods have problems such as the need to add additional reagents, long reaction period and low product yield.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a synthesis method of 2, 2-dimethoxy acetaldehyde, so as to solve the problems of the existing method that additional reagents are required to be added, the reaction period is long, the product yield is low and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for synthesizing 2, 2-dimethoxy acetaldehyde, which comprises the following steps:
Step 1, dewatering an industrial 40% glyoxal aqueous solution, namely pumping the industrial 40% glyoxal aqueous solution into a thin film evaporator, carrying out vacuum dewatering, adding methanol into the dewatered glyoxal when the weight ratio of the glyoxal in the dewatered glyoxal is 55-65%, and then pumping the mixture into the thin film evaporator to carry out vacuum dewatering, and stopping dewatering when the weight ratio of the glyoxal in the dewatered glyoxal alcohol solution is 75-80%, thus obtaining a qualified dewatered glyoxal alcohol solution;
Step 2, synthesizing 2, 2-dimethoxy acetaldehyde, namely adding methanol into a reaction kettle filled with a dehydrated glyoxal alcohol solution, adding saccharin N-sulfonate, and carrying out dehydration reaction to obtain 2, 2-dimethoxy acetaldehyde;
the structural formula of the saccharin N-sulfonate is as follows: wherein R is hydrogen or nitro.
The invention also comprises the following technical characteristics:
specifically, in the step 1, the working temperature of the thin film evaporator is 50-90 ℃.
Specifically, in the step 1, the working pressure of the thin film evaporator is 10-150 mbar.
Specifically, in the step 2, the molar ratio of the dehydrated glyoxal, the methanol and the saccharin N-sulfonate is 1:5-20:0.001-0.05.
Specifically, in the step 2, the molar ratio of the dehydrated glyoxal, the methanol and the saccharin N-sulfonate is 1:8-15:0.001-0.01.
Specifically, in the step 2, the synthesis reaction temperature is 40-85 ℃.
Specifically, in the step 2, the synthesis reaction temperature is 65 ℃ and the reaction time is 5 hours.
Compared with the prior art, the invention has the following technical effects:
Compared with the patent CN 1l84801A and the patent CN 101676252A, the method has the advantages that the method does not need to add extra auxiliary agents, compared with the patent CN 103242145A, the method uses the novel N-sulfonic acid saccharin catalyst, the reaction time is obviously shortened, and compared with the patent yield, the yield of the finally obtained 2, 2-dimethoxy acetaldehyde can reach more than 70 percent.
Detailed Description
The invention provides a method for synthesizing 2, 2-dimethoxy acetaldehyde, which comprises the steps of firstly carrying out vacuum dehydration on industrial 40% glyoxal aqueous solution by a thin film evaporator, adding a certain amount of methanol into the dehydrated glyoxal solution after the dehydration is qualified, carrying out vacuum dehydration again, then taking the dehydrated glyoxal alcohol solution as a reaction raw material, supplementing a required amount of methanol, and carrying out dehydration by taking N-sulfonic acid saccharin as a catalyst to prepare 2, 2-dimethoxy acetaldehyde reaction liquid. The structural formula of the 2, 2-dimethoxy acetaldehyde is shown as a formula (I), the structural formula of the N-sulfonic acid saccharin is shown as a formula (II), and R in the formula (II) is hydrogen or nitro.
The method specifically comprises the following steps:
(1) The industrial 40% glyoxal aqueous solution dehydration treatment comprises the steps of pumping the industrial 40% glyoxal aqueous solution into a film evaporator, carrying out vacuum dehydration at a certain temperature, adding a certain amount of methanol into the dehydrated glyoxal when the weight ratio of glyoxal in the dehydrated glyoxal is 55-65% (glyoxal weight ratio=glyoxal/(glyoxal+water) ×100%), and then pumping into the film evaporator for carrying out vacuum dehydration, and stopping dehydration when the weight ratio of glyoxal in the dehydrated glyoxal alcohol solution is 75-80% (glyoxal weight ratio=glyoxal/(glyoxal+water) ×100%), thereby obtaining the qualified dehydrated glyoxal alcohol solution, wherein the working temperature of the film evaporator is 50-90 ℃. The working pressure of the film evaporator is 10-100 mbar.
(2) 2, 2-Dimethoxy acetaldehyde is synthesized by adding calculated amount of methanol into a reaction kettle filled with dehydrated glyoxal alcohol solution, adding N-sulfonic acid saccharin, and carrying out dehydration reaction to obtain 2, 2-dimethoxy acetaldehyde, wherein the molar ratio of glyoxal, methanol and N-sulfonic acid saccharin is 1:5-20:0.001-0.05, and the reaction temperature is 40-85 ℃.
Preferably, the molar ratio of glyoxal, methanol and saccharin N-sulfonate is 1:8-15:0.001-0.01. The synthesis reaction temperature is 50-75 ℃.
The following specific embodiments of the present application are provided, and it should be noted that the present application is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical scheme of the present application fall within the protection scope of the present application.
Example 1:
The embodiment provides a synthetic method of 2, 2-dimethoxy acetaldehyde, which is to check whether a film evaporator and a collecting kettle are normal, then sequentially starting a cooling tower for circulation, an oil bath for circulation heating, and a vacuum pump for pumping 100kg of 40% glyoxal aqueous solution into the film evaporator at a certain flow rate for dehydration when the working temperature of the film evaporator of 1m 2 reaches 65 ℃ and the working pressure reaches 20mbar to obtain 69.1kg of 57.3% glyoxal aqueous solution, adding 9.8kg of methanol into the glyoxal aqueous solution, and pumping the film evaporator again for dehydration to obtain 58.5kg of 75.3% glyoxal methanol solution.
58.5Kg of 75.3% glyoxal methanol solution, 210.8kg of methanol and 181.5g of saccharin N-sulfonate were added to a 500L reaction vessel, and the reaction was carried out at 65℃for 5 hours with a heat preservation reaction, and the yield of 2, 2-dimethoxyacetaldehyde was 73.1%.
Example 2:
The embodiment provides a synthetic method of 2, 2-dimethoxy acetaldehyde, which is to check whether a film evaporator and a collecting kettle are normal, then sequentially starting a cooling tower for circulation, an oil bath for circulation heating, and a vacuum pump for pumping 100kg of 40% glyoxal aqueous solution into the film evaporator at a certain flow rate for dehydration when the working temperature of the film evaporator of 1m 2 reaches 70 ℃ and the working pressure reaches 20mbar to obtain 65.6kg of 60.7% glyoxal aqueous solution, adding 8.6kg of methanol into the glyoxal aqueous solution, and pumping the film evaporator again for dehydration to obtain 56.8kg of 75.7% glyoxal methanol solution.
56.8Kg of 75.7% glyoxal methanol solution, 212.1kg of methanol and 181.5g of saccharin N-sulfonate were added to a 500L reaction vessel, and the reaction was carried out at 65℃for 5 hours with a heat preservation reaction, and the yield of 2, 2-dimethoxy acetaldehyde was 74.5%.
Example 3:
The embodiment provides a synthetic method of 2, 2-dimethoxy acetaldehyde, which is to check whether a film evaporator and a collecting kettle are normal, then sequentially starting a cooling tower for circulation, an oil bath for circulation heating, and a vacuum pump for pumping 100kg of 40% glyoxal aqueous solution into the film evaporator at a certain flow rate for dehydration when the working temperature of the film evaporator of 1m 2 reaches 70 ℃ and the working pressure reaches 10mbar to obtain 63.9kg of 62.1% glyoxal aqueous solution, adding 8.1kg of methanol into the glyoxal aqueous solution, and pumping the film evaporator again for dehydration to obtain 53.1kg of 79.9% glyoxal methanol solution.
53.1Kg of 75.7% glyoxal methanol solution, 212.6kg of methanol and 181.5g of saccharin N-sulfonate were added to a 500L reactor, and the mixture was heated to 65℃for reaction for 5 hours with a heat preservation reaction, and the yield of 2, 2-dimethoxyacetaldehyde was 73.8%.
Example 4:
The embodiment provides a synthetic method of 2, 2-dimethoxy acetaldehyde, which is to check whether a film evaporator and a collecting kettle are normal, then sequentially starting a cooling tower for circulation, an oil bath for circulation heating, and a vacuum pump for pumping 100kg of 40% glyoxal aqueous solution into the film evaporator at a certain flow rate for dehydration when the working temperature of the film evaporator of 1m 2 reaches 65 ℃ and the working pressure reaches 20mbar to obtain 69.1kg of 57.3% glyoxal aqueous solution, adding 9.8kg of methanol into the glyoxal aqueous solution, and pumping the film evaporator again for dehydration to obtain 58.5kg of 75.3% glyoxal methanol solution.
58.5Kg of 75.3% glyoxal methanol solution, 210.8kg of methanol and 212.6g of 6-nitro-N-sulfonic acid saccharin are added into a 500L reaction kettle, and the mixture is heated to 65 ℃ for heat preservation reaction for 5 hours, and the yield of 2, 2-dimethoxy acetaldehyde is 79.7%.
Comparative example:
The comparative example is that in the prior art, patent CN 1l84801A adopts glyoxal, glyoxal diacetal and methanol to react under the catalysis of an acid resin to prepare 2, 2-dimethoxy acetaldehyde, and patent CN 101676252A adopts glyoxal, corresponding ester of methanol and methanol to react under the catalysis of an acid resin to prepare 2, 2-dimethoxy acetaldehyde.
Compared with the comparative example, the method has the advantages that no additional auxiliary agent is needed, the novel N-sulfonic acid saccharin catalyst is used, the reaction time is obviously shortened, and the yield of the finally obtained 2, 2-dimethoxy acetaldehyde can reach more than 70%.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202311545596.9A CN117700312B (en) | 2023-11-20 | 2023-11-20 | Synthesis method of 2, 2-dimethoxy acetaldehyde |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311545596.9A CN117700312B (en) | 2023-11-20 | 2023-11-20 | Synthesis method of 2, 2-dimethoxy acetaldehyde |
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| CN117700312A CN117700312A (en) | 2024-03-15 |
| CN117700312B true CN117700312B (en) | 2025-08-19 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184801A (en) * | 1996-12-11 | 1998-06-17 | 巴斯福股份公司 | Prenpn. of glyoxal mono acetal |
| CN101676252A (en) * | 2008-09-16 | 2010-03-24 | 上海华谊集团上硫化工有限公司 | Method for preparing acetal by using glyoxal |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10149063A1 (en) * | 2001-10-05 | 2003-04-17 | Basf Ag | Process for the preparation of diacetals of glyoxal |
| CN103242145A (en) * | 2013-04-27 | 2013-08-14 | 南京工业大学 | Method for preparing glyoxal monoacetal and diacetal from glyoxal |
| CN111393270A (en) * | 2020-04-23 | 2020-07-10 | 斯爱玲 | Preparation method of 2, 2-dimethoxyacetaldehyde |
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2023
- 2023-11-20 CN CN202311545596.9A patent/CN117700312B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184801A (en) * | 1996-12-11 | 1998-06-17 | 巴斯福股份公司 | Prenpn. of glyoxal mono acetal |
| CN101676252A (en) * | 2008-09-16 | 2010-03-24 | 上海华谊集团上硫化工有限公司 | Method for preparing acetal by using glyoxal |
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| CN117700312A (en) | 2024-03-15 |
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