CN105272849A - Synthetic method of glyoxylic ester - Google Patents
Synthetic method of glyoxylic ester Download PDFInfo
- Publication number
- CN105272849A CN105272849A CN201410271972.4A CN201410271972A CN105272849A CN 105272849 A CN105272849 A CN 105272849A CN 201410271972 A CN201410271972 A CN 201410271972A CN 105272849 A CN105272849 A CN 105272849A
- Authority
- CN
- China
- Prior art keywords
- acid
- synthetic method
- glyoxylic
- oxoethanoic
- reaction
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of chemical engineering, especially to a synthetic method of glyoxylic ester. According to the synthetic method, glyoxalic acid and alcohol undergo an esterification reaction under catalysis of a catalyst in the presence of a water-carrying agent so as to obtain glyoxylic ester. The catalyst is acid, and the water-carrying agent is hydrocarbon. By the synthetic method, yield of a route product is high, content of a gas phase is high, and side reaction is few. There is no need to use heavy metal or other oxidizing agent. The reaction process is safer, and environmental pollution is avoided. Reaction materials are simple and easily available and are common technological raw materials. By the synthetic scheme, synthesis of glyoxylic ester can be industrialized. The synthetic method has cost advantage. Cost of glyoxylic ester is greatly reduced. The synthetic method provides conditions for slathering glyoxylic ester at the industrial level. In addition, quality of the product is better than quality of a commercially available reagent, and gas phase content of the product is far higher than gas phase content 92% of a commercially available reagent.
Description
Technical field
The present invention relates to chemical field, particularly the synthetic method of glyoxylic ester.
Background technology
Glyoxylic acid ethyl ester is a kind of common fine chemicals, CAS:924-44-7, its aldehyde radical has very high chemically reactive, and the polyreaction of self easily occurs, therefore commercially available glyoxylic acid ethyl ester is that 50% toluene solution is polymerized to prevent it, is mainly used in medicine intermediate, material intermediate.Glyoxylic ester is the dulcet sticky mass of a kind of tool extracted from plant, because it has aldehyde radical and ester group simultaneously, therefore be a kind of important chemical intermediate in organic synthesis, series of chemical can be carried out, be widely used in the synthesis of medical medicine, varnish dyestuff, plastics, essence and flavoring agent, industrial chemical intermediate, such as, prepare vanirone, vanillin food grade,1000.000000ine mesh and wallantoin etc.
The synthetic method of the glyoxylic ester of bibliographical information has a variety of, adopts inorganic oxidizer oxidation diester tartaric acid used (J.Chem.Soc., 1951,1068-1069 and CN1696106A), maleic acid ester and fumarate (J.Org.Chem., 2001,66 (13), 4504-4510; J.Org.Chem., 1986,51 (16), 3213-3214 and TetrahedronLett., 1966,7 (36), 4273-4278) be the common method preparing glyoxylic ester, but only have a few to have reference to its commercial synthesis.
Scheme one:
This method is RobertBruceMoffett(Org.Synth.1972,52,39) use Cl
2cHCOOH is Material synthesis glyoxylic acid ethyl ester.The raw material of this method easily obtains, and product is also more single.But the process reaction that raw material removes ethyl is difficult to carry out thoroughly, and there is ester hydrolysis product, and product content is difficult to promote, and overall yield is lower.
FrankwolfandJohnWeiJlard(Synthesis, 1972,1972 (3), 136-138) proposition such as:
This reaction product is single, without peroxidation phenomenon, and comparatively scheme one productive rate higher (77%-87%).But Pb (OCOCH
3)
4preparation have certain difficulty, lead salt is too large again to the pollution of environment, therefore constrains its industrialized development and application.
The Liu Hongjian of Southeast China University, Wang Dongren research is as follows:
Advantage of this reaction is apparent, and oxidant potassium permanganate has the inexpensive and advantage be easy to get, but because it has snperoxiaized effect, unsaturated olefin can be oxidized to carboxylic acid.Therefore the development of this reaction is restricted.In order to suppress its peroxidation, the people such as WiberK.B have been considerable work (J.Am.Chem.Soc., 1957,79 (9), 2281 – 2283; J.Am.Chem.Soc., 1982,104 (21), pp5826 – 5828; J.Am.Chem.Soc., 1982,104 (19), 5076 – 5081; J.Am.Chem.Soc., 1982,104 (19), 5076 – 5081;
j.Org.Chem., 1986,
51(16), 3213 – 3214).And under optimum reaction condition, productive rate is 47.6% when utilizing this method to prepare glyoxylic acid ethyl ester.Such yield can not meet its industrialized demand far away, and reaction process needs to use strong oxidizer, and side reaction is many, and the product purity obtained is low.
Comprehensive above route, all there is the shortcoming that cost of material is expensive, catalyzer expensive person synthesis yield is low in the scheme of existing report, causes synthesis cost high, be difficult to realize industrialization.Use the inorganic oxidizer such as plumbic acetate, potassium permanganate, price is more expensive and environmental pollution serious, is unfavorable for cleanly production.The process reaction that raw material removes ethyl is difficult to carry out thoroughly, and there is ester hydrolysis product, and product content is difficult to promote.Oxidation style itself easily produces side reaction, produces impurity, and designs the separation problem of reaction solvent and glyoxylic ester, cause product content on the low side, and the gas phase content (deduction toluene peak) of current commercially available glyoxylic acid ethyl ester mostly is about 92%, and content is lower.Therefore, provide that a kind of yield is high, high, the pollution-free synthetic method being suitable for the glyoxylic ester of suitability for industrialized production of gas phase content.
Summary of the invention
In view of this, the route product yield that this synthetic method provided by the invention adopts is high, gas phase content is high, and side reaction is few.Without the need to using heavy metal or other oxygenants, reaction process is safer, and avoids environmental pollution, is suitable for industrialized production.
In order to realize foregoing invention object, the invention provides following technical scheme:
The present invention puies forward the synthetic method of having encircleed a kind of glyoxylic ester, under water entrainer existent condition, gets oxoethanoic acid and alcohol, under the catalysis of catalyzer, esterification occurs, to obtain final product;
Catalyzer is acid;
Water entrainer is hydrocarbon.
In some embodiments of the invention, alcohol is selected from ethanol.
As preferably, the mol ratio of oxoethanoic acid and alcohol is 1:2 ~ 1.
In some embodiments of the invention, the mass ratio of oxoethanoic acid and catalyzer is 1:0.2 ~ 0.01.
In some embodiments of the invention, the mass ratio of oxoethanoic acid and water entrainer is 1:3 ~ 0.5.
In some embodiments of the invention, catalyzer can use and common are machine acid or mineral acid realization, can be hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, tosic acid or methylsulfonic acid.
This esterification process uses water entrainer that the water that reaction generates is isolated reaction system, and reaction process is carried out thoroughly.In some embodiments of the invention, water entrainer is toluene, benzene, normal hexane, hexanaphthene.
In some embodiments of the invention, oxoethanoic acid is aqueous glyoxylic acid or glyoxylic acid hydrate.
In some embodiments of the invention, glyoxylic acid hydrate is a glyoxylic acid.
In some embodiments of the invention, in aqueous glyoxylic acid, the mass concentration of oxoethanoic acid is 10% ~ 80%.
In some embodiments of the invention, the temperature of esterification is the reflux temperature of described water entrainer.
As preferably, the temperature of esterification is 60 ~ 115 DEG C.
In some embodiments of the invention, the step of rectifying is also comprised after esterification.The crude reaction obtained can improve purity through rectifying.
In some embodiments of the invention, the vacuum tightness of rectifying is 15mmHg, and rectifying extraction temperature is 65 ~ 68 DEG C (theoretical values 64 ~ 66.5 DEG C).
The present invention puies forward the synthetic method of having encircleed a kind of glyoxylic ester, under water entrainer existent condition, gets oxoethanoic acid and alcohol, under the catalysis of catalyzer, esterification occurs, to obtain final product; Catalyzer is acid; Water entrainer is hydrocarbon.The route product yield that this synthetic method adopts is high, gas phase content is high, and side reaction is few.Without the need to using heavy metal or other oxygenants, reaction process is safer, and avoids environmental pollution.Reaction raw materials is simple, and being easy to get, is common raw materials technology, adopts this synthetic schemes, enables the synthesis of glyoxylic ester realize industrialization.Have cost advantage, make the cost of glyoxylic ester realize significantly reducing, for its a large amount of uses on industrial level provide condition, and quality product is better than commercially available reagent, far above the gas phase content of commercial reagent 92%.
Accompanying drawing explanation
Fig. 1 shows glyoxylic acid ethyl ester prepared by embodiment 1
1hNMR schemes;
Fig. 2 shows the infrared spectrum of glyoxylic acid ethyl ester prepared by embodiment 1;
Fig. 3 shows the vapor detection spectrogram of commercially available product glyoxylic acid ethyl ester toluene solution;
Fig. 4 shows the vapor detection collection of illustrative plates of glyoxylic acid ethyl ester prepared by embodiment 1.
Embodiment
The invention discloses a kind of synthetic method of glyoxylic ester, those skilled in the art can use for reference present disclosure, and suitable improving technique parameter realizes.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are all deemed to be included in the present invention.Method of the present invention and application are described by preferred embodiment, related personnel obviously can not depart from content of the present invention, spirit and scope methods and applications as herein described are changed or suitably change with combination, realize and apply the technology of the present invention.
In the synthetic method of glyoxylic ester provided by the invention, raw materials used and reagent all can be buied by market.
Below in conjunction with embodiment, set forth the present invention further:
the synthesis of embodiment 1 glyoxylic acid ethyl ester
20% aqueous glyoxylic acid 740g(2mol is added) in 1L reaction flask, water is steamed in decompression, and steam until anhydrous, oxoethanoic acid dewaters complete, after concentrated oxoethanoic acid cooling in question response bottle, again by ethanol 92g(2mol), 1% of tosic acid 1.48g(oxoethanoic acid quality), 0.5 times of toluene 74g(oxoethanoic acid quality), drop in this reaction flask, open cold heating jacket, reaction solution in bottle is heated to 60 DEG C, reacts.In reaction process, point water, separates until anhydrous, continues Distillation recovery toluene.After toluene steams, be cooled to less than 25 DEG C.Above-mentioned residual reaction solution is carried out underpressure distillation, and maintenance system vacuum tightness is 13-15mmHg, receives 65 ~ 68 DEG C of cuts (theoretical value 64 ~ 66.5 DEG C), obtains product.Through underpressure distillation, obtain pale yellow viscous liquid 155.32g.Theoretical yield is 204.18g, product yield 76.07%, and gas phase content is 96.53%.
the synthesis of embodiment 2 glyoxylic acid ethyl ester
10% aqueous glyoxylic acid 1480g(2mol is added) in 1L reaction flask, water is steamed in decompression, and steam until anhydrous, oxoethanoic acid dewaters complete, after concentrated oxoethanoic acid cooling in question response bottle, again by ethanol 110.4g(2.4mol), 2% of hydrochloric acid 2.96g(oxoethanoic acid quality), 1 times of toluene 148g(oxoethanoic acid quality), drop in this reaction flask, open cold heating jacket, reaction solution in bottle is heated to 65 DEG C, reacts.In reaction process, point water, separates until anhydrous, continues Distillation recovery toluene.After toluene steams, be cooled to less than 25 DEG C.Above-mentioned residual reaction solution is carried out underpressure distillation, and maintenance system vacuum tightness is 15mmHg, receives 65 ~ 68 DEG C of cuts (theoretical value 64 ~ 66.5 DEG C), obtains product.Through underpressure distillation, obtain pale yellow viscous liquid 159.93g.Theoretical yield is 204.18g, product yield 78.33%, and gas phase content is 96.73%.
the synthesis of embodiment 3 glyoxylic acid ethyl ester
Solid acetaldehyde acid 184.1g(2.5mol is added) in 1L reaction flask, again by ethanol 128.8g(2.8mol), 3% of phosphoric acid 5.92g(oxoethanoic acid quality), 1.2 times of normal hexane 222g(oxoethanoic acid quality), drop in this reaction flask, open cold heating jacket, reaction solution in bottle is heated to backflow 70 DEG C, reacts.In reaction process, point water, separates until anhydrous, continues Distillation recovery normal hexane.After normal hexane steams, be cooled to less than 25 DEG C.Above-mentioned residual reaction solution is carried out underpressure distillation, and maintenance system vacuum tightness is 15mmHg, receives 65 ~ 68 DEG C of cuts (theoretical value 64 ~ 66.5 DEG C), obtains product.Through underpressure distillation, obtain pale yellow viscous liquid 155.54g.Theoretical yield is 204.18g, product yield 76.54%, and gas phase content is 97.15%.
the synthesis of embodiment 4 glyoxylic acid ethyl ester
A glyoxylic acid 184.1g(2.5mol is added) in 1L reaction flask, again by ethanol 147.2g(3.2mol), 5% of sulfuric acid 8.88g(oxoethanoic acid quality), 1.6 times of hexanaphthene 296g(oxoethanoic acid quality), drop in this reaction flask, open cold heating jacket, reaction solution in bottle is heated to backflow 75 DEG C, reacts.In reaction process, point water, separates until anhydrous, continues Distillation recovery hexanaphthene.After hexanaphthene steams, be cooled to less than 25 DEG C.Above-mentioned residual reaction solution is carried out underpressure distillation, and maintenance system vacuum tightness is 15mmHg, receives 65 ~ 68 DEG C of cuts (theoretical value 64 ~ 66.5 DEG C), obtains product.Through underpressure distillation, obtain pale yellow viscous liquid 153.74g.Theoretical yield is 204.18g, product yield 75.30%, and gas phase content is 95.53%.
the synthesis of embodiment 5 glyoxylic acid ethyl ester
80% aqueous glyoxylic acid 185g(2mol is added) in 1L reaction flask, water is steamed in decompression, and steam until anhydrous, oxoethanoic acid dewaters complete, after concentrated oxoethanoic acid cooling in question response bottle, again by ethanol 165.6g(3.6mol), 8% of nitric acid 11.84g(oxoethanoic acid quality), 2.5 times of benzene 370g(oxoethanoic acid quality), drop in this reaction flask, open cold heating jacket, reaction solution in bottle is heated to backflow 80 DEG C, reacts.In reaction process, point water, separates until anhydrous, continues Distillation recovery benzene.After benzene steams, be cooled to less than 25 DEG C.Above-mentioned residual reaction solution is carried out underpressure distillation, and maintenance system vacuum tightness is 15mmHg, receives 65 ~ 68 DEG C of cuts (theoretical value 64 ~ 66.5 DEG C), obtains product.Through underpressure distillation, obtain pale yellow viscous liquid 150.11g.Theoretical yield is 204.18g, product yield 73.52%, and gas phase content is 96.82%.
the synthesis of embodiment 6 glyoxylic acid ethyl ester
40% aqueous glyoxylic acid 370g(2mol is added) in 1L reaction flask, water is steamed in decompression, and steam until anhydrous, oxoethanoic acid dewaters complete, after concentrated oxoethanoic acid cooling in question response bottle, again by ethanol 184g(4mol), 10% of tosic acid 14.8g(oxoethanoic acid quality), 3 times of toluene 444g(oxoethanoic acid quality), drop in this reaction flask, open cold heating jacket, reaction solution in bottle is heated to backflow 85 DEG C, reacts.In reaction process, point water, separates until anhydrous, continues Distillation recovery toluene.After toluene steams, be cooled to less than 25 DEG C.Above-mentioned residual reaction solution is carried out underpressure distillation, and maintenance system vacuum tightness is 15mmHg, receives 65 ~ 68 DEG C of cuts (theoretical value 64 ~ 66.5 DEG C), obtains product.Through underpressure distillation, obtain pale yellow viscous liquid 156.81g.Theoretical yield is 204.18g, product yield 76.80%, and gas phase content is 97.02%.
the synthesis of embodiment 7 glyoxylic acid ethyl ester
60% aqueous glyoxylic acid 246.7g(2mol is added) in 1L reaction flask, water is steamed in decompression, and steam until anhydrous, oxoethanoic acid dewaters complete, after concentrated oxoethanoic acid cooling in question response bottle, again by ethanol 92g(2mol), 12% of methylsulfonic acid 17.76g(oxoethanoic acid quality), 0.5 times of toluene 74g(oxoethanoic acid quality), drop in this reaction flask, open cold heating jacket, reaction solution in bottle is heated to backflow 90 DEG C, reacts.In reaction process, point water, separates until anhydrous, continues Distillation recovery toluene.After toluene steams, be cooled to less than 25 DEG C.Above-mentioned residual reaction solution is carried out underpressure distillation, and maintenance system vacuum tightness is 15mmHg, receives 65 ~ 68 DEG C of cuts (theoretical value 64 ~ 66.5 DEG C), obtains product.Through underpressure distillation, obtain pale yellow viscous liquid 160.93g.Theoretical yield is 204.18g, product yield 78.82%, and gas phase content is 96.82%.
the synthesis of embodiment 8 glyoxylic acid ethyl ester
50% aqueous glyoxylic acid 296g(2mol is added) in 1L reaction flask, water is steamed in decompression, and steam until anhydrous, oxoethanoic acid dewaters complete, after concentrated oxoethanoic acid cooling in question response bottle, again by ethanol 110.4g(2.4mol), 14% of hydrochloric acid 20.72g(oxoethanoic acid quality), 1 times of toluene 148g(oxoethanoic acid quality), drop in this reaction flask, open cold heating jacket, reaction solution in bottle is heated to backflow 95 DEG C, reacts.In reaction process, point water, separates until anhydrous, continues Distillation recovery toluene.After toluene steams, be cooled to less than 25 DEG C.Above-mentioned residual reaction solution is carried out underpressure distillation, and maintenance system vacuum tightness is 15mmHg, receives 65 ~ 68 DEG C of cuts (theoretical value 64 ~ 66.5 DEG C), obtains product.Through underpressure distillation, obtain pale yellow viscous liquid 159.38g.Theoretical yield is 204.18g, product yield 78.06%, and gas phase content is 96.45%.
the synthesis of embodiment 9 glyoxylic acid ethyl ester
Solid acetaldehyde acid 184.1g(2.5mol is added) in 1L reaction flask, again by ethanol 128.8g(2.8mol), 16% of methylsulfonic acid 23.68g(oxoethanoic acid quality), 1.5 times of normal hexane 276.2g(oxoethanoic acid quality), drop in this reaction flask, open cold heating jacket, reaction solution in bottle is heated to backflow 100 DEG C, reacts.In reaction process, point water, separates until anhydrous, continues Distillation recovery normal hexane.After normal hexane steams, be cooled to less than 25 DEG C.Above-mentioned residual reaction solution is carried out underpressure distillation, and maintenance system vacuum tightness is 15mmHg, receives 65 ~ 68 DEG C of cuts (theoretical value 64 ~ 66.5 DEG C), obtains product.Through underpressure distillation, obtain pale yellow viscous liquid 158.04g.Theoretical yield is 204.18g, product yield 77.40%, and gas phase content is 97.32%.
the synthesis of embodiment 10 glyoxylic acid ethyl ester
A glyoxylic acid 184.1g(2.5mol is added) in 1L reaction flask, again by ethanol 147.2g(3.2mol), 18% of phosphoric acid 26.64g(oxoethanoic acid quality), 2.5 times of hexanaphthene 460.3g(oxoethanoic acid quality), drop in this reaction flask, open cold heating jacket, reaction solution in bottle is heated to backflow 110 DEG C, reacts.In reaction process, point water, separates until anhydrous, continues Distillation recovery hexanaphthene, after hexanaphthene steams, is cooled to less than 25 DEG C.Above-mentioned residual reaction solution is carried out underpressure distillation, and maintenance system vacuum tightness is 15mmHg, receives 65 ~ 68 DEG C of cuts (theoretical value 64 ~ 66.5 DEG C), obtains product.Through underpressure distillation, obtain pale yellow viscous liquid 155.03g.Theoretical yield is 204.18g, product yield 75.93%, and gas phase content is 95.98%.
the synthesis of embodiment 11 glyoxylic acid ethyl ester
30% aqueous glyoxylic acid 493g(2mol is added) in 1L reaction flask, water is steamed in decompression, and steam until anhydrous, oxoethanoic acid dewaters complete, after concentrated oxoethanoic acid cooling in question response bottle, again by ethanol 184g(4mol), 20% of methylsulfonic acid 29.6g(oxoethanoic acid quality), 3 times of benzene 444g(oxoethanoic acid quality), drop in this reaction flask, open cold heating jacket, reaction solution in bottle is heated to backflow 115 DEG C, reacts.In reaction process, point water, separates until anhydrous, continues Distillation recovery benzene.After benzene steams, be cooled to less than 25 DEG C.Above-mentioned residual reaction solution is carried out underpressure distillation, and maintenance system vacuum tightness is 15mmHg, receives 65 ~ 68 DEG C of cuts (theoretical value 64 ~ 66.5 DEG C), obtains product.Through underpressure distillation, obtain pale yellow viscous liquid 155.03g.Theoretical yield is 204.18g, product yield 77.52%, and gas phase content is 96.94%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a synthetic method for glyoxylic ester, is characterized in that, under water entrainer existent condition, gets oxoethanoic acid and alcohol, under the catalysis of catalyzer, esterification occurs, to obtain final product;
Described catalyzer is acid;
Described water entrainer is hydrocarbon.
2. synthetic method according to claim 1, is characterized in that, described alcohol is selected from ethanol.
3. synthetic method according to claim 1, is characterized in that, the mol ratio of described oxoethanoic acid and described ethanol is 1:2 ~ 1.
4. synthetic method according to claim 1, is characterized in that, the mass ratio of described oxoethanoic acid and described catalyzer is 1:0.2 ~ 0.01.
5. synthetic method according to claim 1, is characterized in that, the mass ratio of described oxoethanoic acid and described water entrainer is 1:3 ~ 0.5.
6. synthetic method according to claim 1, is characterized in that, described catalyzer is selected from hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, tosic acid or methylsulfonic acid.
7. synthetic method according to claim 1, is characterized in that, described water entrainer is normal hexane, hexanaphthene, toluene or benzene.
8. synthetic method according to claim 1, is characterized in that, described oxoethanoic acid is selected from aqueous glyoxylic acid or glyoxylic acid hydrate; Described glyoxylic acid hydrate is a glyoxylic acid; In described aqueous glyoxylic acid, the mass concentration of oxoethanoic acid is 10% ~ 80%.
9. synthetic method according to claim 1, is characterized in that, the temperature of described esterification is 60 ~ 115 DEG C.
10. synthetic method according to claim 1, is characterized in that, also comprises the step of rectifying after described esterification; The vacuum tightness of described rectifying is 15mmHg, and the temperature of described rectifying is 65 ~ 68 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410271972.4A CN105272849A (en) | 2014-06-18 | 2014-06-18 | Synthetic method of glyoxylic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410271972.4A CN105272849A (en) | 2014-06-18 | 2014-06-18 | Synthetic method of glyoxylic ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105272849A true CN105272849A (en) | 2016-01-27 |
Family
ID=55142752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410271972.4A Pending CN105272849A (en) | 2014-06-18 | 2014-06-18 | Synthetic method of glyoxylic ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105272849A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209829A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for producing glyoxylic ester |
| CN113563193A (en) * | 2020-08-24 | 2021-10-29 | 江苏禾本生化有限公司 | New preparation method of fenisobromolate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6150941A (en) * | 1984-08-17 | 1986-03-13 | Nippon Synthetic Chem Ind Co Ltd:The | Production of glyoxylic ester |
| JP2005170880A (en) * | 2003-12-12 | 2005-06-30 | Takasago Internatl Corp | Method for producing glyoxylate |
| JP2008156333A (en) * | 2006-09-14 | 2008-07-10 | Okada Giken:Kk | New diglyoxylic acid ester, new glyoxylic acid alkoxyalkyl hemiacetal ester, and deodorant containing mono- and di-glyoxylic acid esters and glyoxylic acid hemiacetal esters |
| CN101274892A (en) * | 2008-05-04 | 2008-10-01 | 浙江教育学院 | Method for preparing L-menthol glyoxylic ester monohydrate with solid acid as catalyst |
-
2014
- 2014-06-18 CN CN201410271972.4A patent/CN105272849A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6150941A (en) * | 1984-08-17 | 1986-03-13 | Nippon Synthetic Chem Ind Co Ltd:The | Production of glyoxylic ester |
| JP2005170880A (en) * | 2003-12-12 | 2005-06-30 | Takasago Internatl Corp | Method for producing glyoxylate |
| JP2008156333A (en) * | 2006-09-14 | 2008-07-10 | Okada Giken:Kk | New diglyoxylic acid ester, new glyoxylic acid alkoxyalkyl hemiacetal ester, and deodorant containing mono- and di-glyoxylic acid esters and glyoxylic acid hemiacetal esters |
| CN101274892A (en) * | 2008-05-04 | 2008-10-01 | 浙江教育学院 | Method for preparing L-menthol glyoxylic ester monohydrate with solid acid as catalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209829A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for producing glyoxylic ester |
| CN112209829B (en) * | 2019-07-12 | 2023-08-08 | 中国石油化工股份有限公司 | Method for producing glyoxylate |
| CN113563193A (en) * | 2020-08-24 | 2021-10-29 | 江苏禾本生化有限公司 | New preparation method of fenisobromolate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106187735B (en) | The method of diisobutylene carbonylation synthesis pivalic acid and 2,2,4,4- tetramethyl valeric acid | |
| CN108997112B (en) | Preparation method of 4-acetoxyl-2-methyl-2-butenal | |
| CN112898141B (en) | Method for preparing o-methoxybenzaldehyde by using dimethyl carbonate | |
| CN102070575A (en) | New synthesis method of caronic anhydride | |
| CN115894229B (en) | Selective synthesis process of adipic acid monoethyl ester | |
| CN109942407B (en) | Method for synthesizing 9, 10-dihydroxyl octadecanoic acid | |
| CN102206136A (en) | Catalyst-free synthesis method for preparing 3-methyl-3-butylene-1-alcohol | |
| CN103694119A (en) | Preparation method of ethyl 4,4,4-trifluoroacetoacetate | |
| CN105272849A (en) | Synthetic method of glyoxylic ester | |
| CN102942476A (en) | Preparation method of linalyl acetate | |
| CN107473948B (en) | Synthetic method for preparing 3, 5-dichloro-2-pentanone from ethyl acetoacetate | |
| CN113754592A (en) | Preparation method of 2, 4-diamino-6-chloropyrimidine | |
| US3939202A (en) | Process for preparing polyene compounds | |
| CN114349633A (en) | Process for the preparation of diesters of glutaconic acid | |
| CN109593045B (en) | Preparation method of 11-aminoundecanoic acid | |
| CN102863320B (en) | Preparation technology of veratrole | |
| CN104277027A (en) | Preparation method of (R)-propylene carbonate | |
| CN111116339B (en) | Method for artificially synthesizing curcumin and derivatives thereof | |
| CN105348061A (en) | 2-cyclohexene-1-ketone preparation method | |
| CN112624915A (en) | Method for preparing 2, 5-dihydroxyterephthalic acid (DHTA) | |
| CN109796452B (en) | Cyclopenta dihydroquinoline compound and preparation method thereof | |
| CN104292080B (en) | The continuous distillation method of two-(2-chloro isopropyl) ether is extracted from epoxy propane slop | |
| CN115403452B (en) | Preparation method of p-methoxyphenol | |
| CN112341408B (en) | Preparation method of coconut aldehyde | |
| CN114736103B (en) | Method for separating propyl guaiacol and propyl syringol from lignin oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160127 |