CN101659650A - Method of preparing piperonal in one kettle way - Google Patents
Method of preparing piperonal in one kettle way Download PDFInfo
- Publication number
- CN101659650A CN101659650A CN200910196309A CN200910196309A CN101659650A CN 101659650 A CN101659650 A CN 101659650A CN 200910196309 A CN200910196309 A CN 200910196309A CN 200910196309 A CN200910196309 A CN 200910196309A CN 101659650 A CN101659650 A CN 101659650A
- Authority
- CN
- China
- Prior art keywords
- acid
- methylenedioxybenzenes
- kettle way
- piperonal
- 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.)
- Granted
Links
Landscapes
- Hydrogenated Pyridines (AREA)
Abstract
The invention relates to a method of preparing piperonal in a one kettle way, which is a technical improvement of using 1,2-(methylenedioxy) benzene as a raw material to synthesize the piperonal. By the measures of selecting a proper solvent, adding an additive, diluting a reaction solution, and the like, the intermediate 3,4-(methylenedioxy) mandelic acid can be directly oxidized without being separated and purified to synthesize the piperonal in the 'one kettle' way. The invention has the characteristics of simple operation, high yield and the like, and both the purity and the quality of theproduct meet the requirements.
Description
Technical field
The present invention relates to a kind of method of preparing piperonal in one kettle way.
Background technology
Piperonal is a kind of important spices, has sweet turnsole fragrance, light little sweet cherry and sunflower fragrance and faint hot perfume, be the security spices that U.S.'s spice extract is made association's approval, and be used to spices and seasonings industry, and the optical brightener of Metal plating, also be the synthesis material of medicine and agricultural chemicals.
The chemical name of piperonal is 3,4-dioxy methylene-benzene formaldehyde.Synthetic method commonly used is with 1, and the 2-methylenedioxybenzenes is a raw material, makes intermediate 3 earlier, obtains through oxidation behind the 4-methylene-dioxy mandelic acid again.Anteroposterior diameter is crossed two-step reaction.
Intermediate 3,4-methylene-dioxy mandelic acid are generally by 1, and 2-methylenedioxybenzenes and oxoethanoic acid react under acidic conditions and make (JP2002114774; JP08059650; CN1400972; WO0127100 etc.).Also can be by 1,2-methylenedioxybenzenes and Paraformaldehyde 96 (JP2003171344) or glyoxalic acid methylester (JP2003171344) react under acidic conditions and make.3,4-methylene-dioxy mandelic acid obtains piperonal through oxidation.Oxidising agent commonly used is nitric acid (EP429316; JP7258246; JP7330755; WO0127100); Other oxygenant is also arranged, as Sodium Persulfate (Organic Process Research ﹠amp in the document; Development, 2000,534-543) carry out the report of oxidizing reaction.
In the aforesaid method, through 1, the intermediate 3 that 2-methylenedioxybenzenes and glyoxalic acid reaction generate, 4-methylene-dioxy mandelic acid often separate by filtering method earlier, but filter operation is unfavorable for using in the industrial production.Improve one's methods as a kind of, after reaction finished, by extracting elder generation with intermediate 3,4-methylene-dioxy mandelic acid separated, and extraction liquid can be directly used in oxidizing reaction (CN 1400972) after neutralization.If 3,4-methylene-dioxy mandelic acid directly carries out oxidizing reaction without separation, can cause containing in the product tens of ppm1,2-methylene-dioxy-4-oil of mirbane is a kind of like this to be difficult to isolating impurity, and it is faint yellow that product is, and influences its quality (CN 1400972)
Summary of the invention
The object of the present invention is to provide a kind of method of preparing piperonal in one kettle way.
The method of the preparing piperonal in one kettle way that the present invention proposes, with 1, the 2-methylenedioxybenzenes is a raw material, adopts " one kettle way " synthesizing piperonal.The present invention is by selecting appropriate solvent and adding additive, and measures such as dilute reaction solution control reaction conditions suppresses side reaction.Can not need separation of intermediates, a step obtains the satisfactory piperonal of purity, has simplified operation.
The method of the preparing piperonal in one kettle way that the present invention proposes, concrete steps are as follows:
(1) addition reaction: under logical nitrogen situation, with 1, the 2-methylenedioxybenzenes is dissolved in the organic acid solvent, is cooled to drip the mixed solution of being made up of oxoethanoic acid and mineral acid after-10～0 ℃, and temperature is controlled at 0～5 ℃, adds the back and continues reaction 24 hours; 1, the mol ratio of 2-methylenedioxybenzenes and oxoethanoic acid is 1: 1.1～1: 3.0,1, and the mol ratio of 2-methylenedioxybenzenes and mineral acid is 1: 1.5～1: 4;
(2) in the reaction mixture that step (1) is generated, add additive, and add water and organic solvent diluting; The add-on of additive is 1,2～10mol% of 2-methylenedioxybenzenes, and the add-on of water is 1-5 a times of mineral acid weight, the add-on of organic solvent is 2-3 a times of organic acid solvent in the step (1);
(3) oxidizing reaction: the reaction mixture after step (2) is handled drips concentrated nitric acid oxidation down at 0～5 ℃, and room temperature reaction 1～1.5 hour is warming up to 40～50 ℃ then and continues reaction 0.5～1 hour.Through aftertreatment, obtain required product, wherein: 1, the mol ratio of 2-methylenedioxybenzenes and nitric acid is 1: 0.7～1: 1.
Among the present invention, organic acid solvent described in the step (1) adopts acetate or formic acid.
Among the present invention, mineral acid described in the step (1) be in sulfuric acid, phosphoric acid or the chlorsulfonic acid etc. any, with sulfuric acid the best.
Among the present invention, additive described in the step (2) is cyclodextrin compounds such as quaternary ammonium compounds such as tetrabutylammonium chloride, triethyl benzyl ammonia chloride or trimethylammonium cetyl chloride ammonium, or beta-cyclodextrin.
Among the present invention, organic solvent is alkane such as normal hexane or hexanaphthene described in the step (2); Aromatic hydrocarbons such as benzene, toluene or dimethylbenzene; Ether compounds such as ether, diisopropyl ether or dibutyl ether; Carbonyl compound such as pentanone or pimelinketone or ethyl acetate, carboxylicesterss such as butylacetate.
Among the present invention, 1, employed in the addition reaction of 2-methylenedioxybenzenes and oxoethanoic acid is 40% aqueous glyoxylic acid.The used in amounts of oxoethanoic acid is suitably excessive, and 1, the mol ratio of 2-methylenedioxybenzenes and oxoethanoic acid was controlled at 1: 1.1～1: 3.0, was advisable with 1: 1.2～1: 1.5.
Among the present invention, described 1, the mol ratio of 2-methylenedioxybenzenes and mineral acid is 1: 2～1: 3.
Among the present invention, 1, after the addition reaction of 2-methylenedioxybenzenes and oxoethanoic acid finishes, adopt the method for doping and dilute reaction solution to suppress side reaction simultaneously, reduce and even avoid impurity 1, the quality product of " one kettle way " synthesizing piperonal is guaranteed in the generation of 2-methylene-dioxy-4-oil of mirbane.
Among the present invention, the add-on of additive is 1,5～10mol% of 2-methylenedioxybenzenes.
Among the present invention, the add-on of water is 2～3 times of mineral acid weight.
Among the present invention with 1, the 2-methylenedioxybenzenes is a raw material, adopt " one kettle way " synthesizing piperonal, by selecting appropriate solvent and adding additive, measures such as dilute reaction solution, intermediate 3,4-methylene-dioxy mandelic acid can directly carry out oxidation without separation, and a step obtains the satisfactory piperonal of quality, the mild condition that responds, characteristics such as easy and simple to handle.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1
In the 2000mL reaction flask, under the situation of logical nitrogen, add 98g (0.8mol) 1,2-methylenedioxybenzenes and 100mL acetate.Be cooled to-10～0 ℃ under stirring, drip the mixed solution of being made up of 180g 40% (1mol) oxoethanoic acid and the 179g vitriol oil, temperature is controlled at 0～5 ℃.Adding the back continues to stir 24 hours.
React the end back and in reaction system, add 4.0gTEBA (triethyl benzyl ammonia chloride), 400mL water and 250mL toluene, and in the time of 0～5 ℃, add the 65g concentrated nitric acid, room temperature reaction is warming up to 40～50 ℃ after 1 hour, continue to react half an hour.Reaction solution is told organic layer after being chilled to room temperature, and water layer extracts (50mL * 2) with toluene.Organic layer is used sodium bicarbonate aqueous solution and washing successively, and toluene is reclaimed in dry back.Underpressure distillation obtains white solid 98g (productive rate 81%), after testing, and product piperonal content 〉=99%.
Embodiment 2
In the 2000mL reaction flask, logical nitrogen adds 98g (0.8mol) 1,2-methylenedioxybenzenes and 80mL acetate.Be cooled to-10～0 ℃ under stirring, drip the mixed solution of being made up of 180g 40% (1mol) oxoethanoic acid and the 179g vitriol oil, temperature is controlled at 0～5 ℃.Adding the back continues to stir 24 hours.
Reaction end back adds the 10g beta-cyclodextrin in reaction system, 400mL water and 250mL toluene, and in the time of 0～5 ℃, add the 65g concentrated nitric acid, room temperature reaction is warming up to 40～50 ℃ after 1 hour, continue to react half an hour.Reaction solution is told organic layer after being chilled to room temperature, and water layer extracts (50mL * 2) with toluene.Organic layer is used sodium bicarbonate aqueous solution and washing successively, and toluene is reclaimed in dry back.Underpressure distillation obtains piperonal 101g (productive rate 84%), is white solid, content 〉=99%.
Embodiment 3
Reaction flask leads to nitrogen, adds 98g (0.8mol) 1,2-methylenedioxybenzenes and 100mL formic acid.Be cooled to-10～0 ℃ under stirring, drip the mixed solution of being made up of 200g 40% (1.2mol) oxoethanoic acid and 200g phosphoric acid, temperature is controlled at 0～5 ℃.Adding the back continues to stir 24 hours.React and finish, add the 10g beta-cyclodextrin in the reaction system, 400mL water and 200mL benzene, and in the time of 0～5 ℃, add the 65g concentrated nitric acid, room temperature reaction is warming up to 40～50 ℃ after 1 hour, continue to react half an hour.Reaction solution is told organic layer after being chilled to room temperature, and water layer extracts with toluene.Organic layer reclaims solvent after washing drying.Underpressure distillation obtains 90g product (productive rate 75%, content 〉=99%).
Embodiment 4
Reaction flask leads to nitrogen, adds 98g (0.8mol) 1,2-methylenedioxybenzenes and 150mL acetate.Be cooled to-10～0 ℃ under stirring, drip the mixed solution of being made up of 175g 40% (1mol) oxoethanoic acid and the 179g vitriol oil, temperature is controlled at 0～5 ℃.Adding the back continues to stir 24 hours.Reaction finishes, and is chilled to 0～5 ℃, adds the 65g concentrated nitric acid, at 40～50 ℃, continues reaction 1.5 hours.Reaction solution be chilled to after the room temperature with in toluene extractive reaction mixture (50mL * 3) organic layer and after, through washing, drying reclaims solvent.Underpressure distillation obtains 92g product (productive rate 87%), and it is faint yellow that product is.
Claims (9)
1, a kind of method of preparing piperonal in one kettle way is characterized in that concrete steps are as follows:
(1) addition reaction: under logical nitrogen situation, with 1, the 2-methylenedioxybenzenes is dissolved in the organic acid solvent, is cooled to drip the mixed solution of being made up of oxoethanoic acid and mineral acid after-10～0 ℃, and temperature is controlled at 0～5 ℃, adds the back and continues reaction 24 hours; 1, the mol ratio of 2-methylenedioxybenzenes and oxoethanoic acid is 1: 1.1～1: 3.0,1, and the mol ratio of 2-methylenedioxybenzenes and mineral acid is 1: 1.5～1: 4;
(2) in the reaction mixture that step (1) is generated, add additive, and add water and organic solvent diluting; The add-on of additive is 1,2～10mol% of 2-MDB, and the add-on of water is 1-5 a times of mineral acid weight, the add-on of organic solvent is 2-3 a times of organic acid solvent in the step (1);
(3) oxidizing reaction: the reaction mixture of handling through step (2) drips concentrated nitric acid oxidation down at 0～5 ℃, room temperature reaction 1～1.5 hour, be warming up to 40～50 ℃ then and continue reaction 0.5～1 hour, through aftertreatment, obtain required product, wherein: 1, the mol ratio of 2-methylenedioxybenzenes and nitric acid is 1: 0.7～1: 1.
2, the method for preparing piperonal in one kettle way according to claim 1 is characterized in that organic acid solvent described in the step (1) adopts acetate or formic acid.
3, the method for preparing piperonal in one kettle way according to claim 1, it is characterized in that mineral acid described in the step (1) be in sulfuric acid, phosphoric acid or the chlorsulfonic acid any.
4, the method for preparing piperonal in one kettle way according to claim 1, it is characterized in that additive described in the step (2) be in tetrabutylammonium chloride, triethyl benzyl ammonia chloride, trimethylammonium cetyl chloride ammonium or the cyclodextrin compounds any.
5, the method for preparing piperonal in one kettle way according to claim 1, it is characterized in that organic solvent described in the step (2) be in normal hexane, hexanaphthene, benzene,toluene,xylene, ether, diisopropyl ether, dibutyl ether, pentanone, pimelinketone, ethyl acetate or the butylacetate any.
6, the method for preparing piperonal in one kettle way according to claim 1 is characterized in that 1, and the mol ratio of 2-methylenedioxybenzenes and oxoethanoic acid is 1: 1.2～1: 1.5.
7, the method for preparing piperonal in one kettle way according to claim 1 is characterized in that describedly 1, and the mol ratio of 2-methylenedioxybenzenes and mineral acid is 1: 2～1: 3.
8, the method for preparing piperonal in one kettle way according to claim 1, the add-on that it is characterized in that additive is 1,5～10mol% of 2-methylenedioxybenzenes.
9, the method for preparing piperonal in one kettle way according to claim 1, the add-on that it is characterized in that water are 2～3 times of mineral acid weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910196309A CN101659650B (en) | 2009-09-24 | 2009-09-24 | Method of preparing piperonal in one kettle way |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910196309A CN101659650B (en) | 2009-09-24 | 2009-09-24 | Method of preparing piperonal in one kettle way |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101659650A true CN101659650A (en) | 2010-03-03 |
| CN101659650B CN101659650B (en) | 2012-09-05 |
Family
ID=41787924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910196309A Expired - Fee Related CN101659650B (en) | 2009-09-24 | 2009-09-24 | Method of preparing piperonal in one kettle way |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101659650B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753831A (en) * | 2016-04-01 | 2016-07-13 | 衢州信步化工科技有限公司 | Refining method for piperonal |
| CN106349209A (en) * | 2016-08-25 | 2017-01-25 | 宿迁市万和泰化工有限公司 | Process for synthesizing heliotropin |
| CN107434798A (en) * | 2016-05-27 | 2017-12-05 | 浙江新和成股份有限公司 | A kind of preparation method of heliotropin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6104196A (en) * | 1995-06-06 | 1996-12-24 | Neurobiological Technologies, Inc. | Novel n-substituted-2-amino-3',4'-methylene-dioxypropiopheno nes |
| TWI291954B (en) * | 2000-02-02 | 2008-01-01 | Ube Industries |
-
2009
- 2009-09-24 CN CN200910196309A patent/CN101659650B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753831A (en) * | 2016-04-01 | 2016-07-13 | 衢州信步化工科技有限公司 | Refining method for piperonal |
| CN107434798A (en) * | 2016-05-27 | 2017-12-05 | 浙江新和成股份有限公司 | A kind of preparation method of heliotropin |
| CN106349209A (en) * | 2016-08-25 | 2017-01-25 | 宿迁市万和泰化工有限公司 | Process for synthesizing heliotropin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101659650B (en) | 2012-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105924623B (en) | A kind of eugenol epoxy resin and the preparation method and application thereof | |
| CN101786948A (en) | Method for preparing 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone | |
| CN101659650B (en) | Method of preparing piperonal in one kettle way | |
| CN101792378B (en) | Method for preparing anisaldehyde | |
| CN107265420B (en) | A method of azanol is prepared by cyclohexanone oxime hydrolysis | |
| CN107540531B (en) | Method for preparing o-chlorocyclohexanone by using cyclohexanone byproduct light oil | |
| CN103880674A (en) | Synthetic process of L-menthyl glyoxylate | |
| CN105348044B (en) | A kind of synthetic method of hemlock extract (S)-Virol A | |
| CN102050712B (en) | Preparation method of anisaldehyde | |
| CN103086979B (en) | Method for preparing imidazole aldehyde | |
| CN109251138A (en) | A kind of preparation method of all natural carbon source raspberry ketone | |
| CN104370830A (en) | Synthetic method of 5-trifluoromethyl uracil | |
| CN107129466B (en) | Synthesis method of 4-chloro-3-methoxy-2-methylpyridine-N-oxide | |
| CN108047032A (en) | By α-ketoglutaric acid to glutaric acid synthetic method | |
| CN108203368A (en) | A kind of production technology of high-quality trimethyl orthoacetate | |
| CN105601610A (en) | Preparation method for monobenzalpenlpentaerythritol | |
| CN106749003B (en) | A kind of preparation method of ethoxyquinoline | |
| CN109336820B (en) | Preparation method of 1H-imidazole-4-carbonitrile | |
| CN103058965A (en) | Preparation method of perfume in furan class | |
| CN109796416A (en) | A kind of synthetic method of 2- acetyl group pyrazine | |
| CN109516911A (en) | A kind of synthetic method of 2,2-dimethylbutyric acid | |
| CN114315527B (en) | Preparation method of resorcinol | |
| CN103030552A (en) | Method for one-time synthesis of 2-phenylpropionic acid by strawberry aldehyde | |
| CN107216308A (en) | A kind of preparation method of piperonal | |
| CN106565634A (en) | Production method for preparing 2,3-epoxypinane through epoxidizing alpha-pinene |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120905 Termination date: 20160924 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |