CN102766131A - Synthetic method of 1, 3-benzodioxole - Google Patents
Synthetic method of 1, 3-benzodioxole Download PDFInfo
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- CN102766131A CN102766131A CN2012102846699A CN201210284669A CN102766131A CN 102766131 A CN102766131 A CN 102766131A CN 2012102846699 A CN2012102846699 A CN 2012102846699A CN 201210284669 A CN201210284669 A CN 201210284669A CN 102766131 A CN102766131 A CN 102766131A
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Abstract
The invention discloses a synthetic method of 1, 3-benzodioxole. Aldehyde ketone and catechol with mass ratio of 1-1.5:1 are added in a three-necked bottle provided with electromagnetic stirring, a condensation pipe and a water segregator, entrainer cyclohexane and per mol aldehyde ketone consumes 2.0-3.0k of catalyst carbon-based solid acid, water generated through reaction and the entrainer cyclohexane are steamed out in azeotropic mode through heating, backflow and stirring, sampling analysis is performed during a reaction process, reaction is performed until no water is left, the mixture enters the water segregator to stay for 2-5 hours, and reaction is stopped. In the synthetic method, the carbon-based solid acid has high catalysis on the catechol and the aldehyde ketone, conversion rate is above 80%, and selectivity is above 95%.
Description
Technical field
The invention belongs to the synthetic field of organic chemistry, be specifically related to a kind of 1, the compound method of 3-Ben Bing dioxolane.
Background technology
1,3-Ben Bing dioxolane is one type of important compound, and its member ring systems is present in many natural compoundss as a complete part, like sesamol, piperine etc.1,3-Ben Bing dioxolane compounds not only can be used as the suppressor factor of thin race monooxygenase, also is widely used in production sterilant or pesticide intermediate, weedicide, oxidation inhibitor, antiseptic-germicide, medicine etc., is important active medicine midbody.Therefore, 1, the synthetic technology of 3-Ben Bing dioxolane compounds receives the attention of each side such as biological chemistry and organic synthesis simultaneously.
At present, domestic relevant 1, the synthetic of 3-Ben Bing dioxolane almost do not appear in the newspapers, and the route of synthesis of external report mainly contains following several: 1, adopt pyrocatechol and react together with dihalide to prepare, but together with the manufacturer of dihalide seldom, cost an arm and a leg; 2, under boron tribromide catalysis, adopt the dimethylacetal (ketone) and the exchange condensation of pyrocatechol to synthesize; 3, in the presence of an acidic catalyst, pyrocatechol and carbonyl compound carry out condensation reaction.Undoubtedly, method 3 can receive general attention.Originally, be to be catalyzer with the Vanadium Pentoxide in FLAKES, in this process, Vanadium Pentoxide in FLAKES is on the one hand as an acidic catalyst, on the other hand also as dewatering agent by mass consumption, therefore, raw material consumption is very big, simultaneously, side reaction is also many.Tosic acid also is widely used in this reaction, under minute water condition, only needs catalytic amount can accomplish reaction, and (8～120h), productive rate is also lower but the reaction times is long.Recently, trimethylchlorosilane, phosphorus trichloride, illiteracy unsticking soil, solid super-strong acid etc. all are used as this catalyst for reaction, but more or less all have some problems.The molecular sieve fool is because its unique catalytic activity and shape selectivity are widely used in many organic synthesis.
Summary of the invention
The invention provides a kind of new 1, the compound method of 3-Ben Bing dioxolane.
In the three-necked bottle that has induction stirring, prolong, water trap; Add people's amount of substance ratio and be 1～1.5: 1 aldehyde ketone and pyrocatechol, the catalyst carbon based solid acid of entrainer hexanaphthene and every mol aldehyde ketone consumption 2.0～3.0g, reflux stirs; Water and entrainer hexanaphthene azeotropic that reaction is produced steam; Sampling analysis in the reaction process, reaction to anhydrous water trap 2～5h, the stopped reaction of getting into again.
Described aldehyde ketone is a kind of in pimelinketone, butanone, acetone, propionic aldehyde, butyraldehyde, isobutyric aldehyde, valeral, isovaleric aldehyde, n-hexyl aldehyde, n-octaldehyde, the phenyl aldehyde, preferred pimelinketone.
Preferred aldehyde ketone is 1.2: 1 with the amount of substance ratio of pyrocatechol.
The consumption of preferred catalyst carbon-based solid acid is every mol aldehyde ketone consumption 2.5g.
Preferred reaction gets into 4h in the water trap again to anhydrous.
Carbon-based solid acid has higher catalytic to pyrocatechol and aldehyde ketone reaction in the compound method of the present invention, and transformation efficiency is all more than 80%, and selectivity is more than 95%.
Embodiment
Below in conjunction with embodiment to of the present invention 1; The compound method of 3-Ben Bing dioxolane is set forth in detail; Thereby protection scope of the present invention is made more explicit defining so that advantage of the present invention and characteristic can be easier to it will be appreciated by those skilled in the art that.
The raw material reagent that the present invention is used: pimelinketone (AR), butanone (AR), acetone (AR), propionic aldehyde (AR), butyraldehyde (AR), isobutyric aldehyde (Merck company), valeral (CP), isovaleric aldehyde (Merck company), n-hexyl aldehyde (Merck company), n-octaldehyde (Fluker company), pyrocatechol (CP), phenyl aldehyde (CP), hexanaphthene (AR).
50g Z 150PH, 35g hydroxyethylsulfonic acid and 500mL deionized water are placed 1000mL Teflon stainless steel cauldron; Behind reaction 4h under 180 ℃ of conditions, cool to room temperature filters; Washing and methyl alcohol are washed, and dry 4h promptly gets black carbon based solid acid 25g under 100 ℃ at last.
Embodiment 1
In having the 100mL three-necked bottle of induction stirring, prolong, water trap, add pimelinketone, butanone, acetone, propionic aldehyde, butyraldehyde, isobutyric aldehyde, valeral, isovaleric aldehyde, n-hexyl aldehyde, n-octaldehyde or the phenyl aldehyde of people 1mol, the 1mol pyrocatechol; The catalyst carbon based solid acid of the hexanaphthene of 30～50ml and 2.0g; Reflux stirs, and water and entrainer hexanaphthene azeotropic that reaction is produced steam sampling analysis in the reaction process; Reaction to the anhydrous about 2h of water trap, the stopped reaction of getting into again.
Embodiment 2
In having the 100mL three-necked bottle of induction stirring, prolong, water trap, add pimelinketone, butanone, acetone, propionic aldehyde, butyraldehyde, isobutyric aldehyde, valeral, isovaleric aldehyde, n-hexyl aldehyde, n-octaldehyde or the phenyl aldehyde of people 1.5mol, the 1mol pyrocatechol; The catalyst carbon based solid acid of the hexanaphthene of 30～50ml and 4.5g; Reflux stirs, and water and entrainer hexanaphthene azeotropic that reaction is produced steam sampling analysis in the reaction process; Reaction to the anhydrous about 5h of water trap, the stopped reaction of getting into again.
Embodiment 3
In having the 100mL three-necked bottle of induction stirring, prolong, water trap, add pimelinketone, butanone, acetone, propionic aldehyde, butyraldehyde, isobutyric aldehyde, valeral, isovaleric aldehyde, n-hexyl aldehyde, n-octaldehyde or the phenyl aldehyde of people 1.2mol, the 1mol pyrocatechol; The catalyst carbon based solid acid of the hexanaphthene of 30～50ml and 3.0g; Reflux stirs, and water and entrainer hexanaphthene azeotropic that reaction is produced steam sampling analysis in the reaction process; Reaction to the anhydrous about 4h of water trap, the stopped reaction of getting into again.
Carbon-based solid acid has higher catalytic to pyrocatechol and aldehyde ketone reaction in the compound method of the present invention, and transformation efficiency is all more than 80%, and selectivity is more than 95%.
Claims (5)
1. the compound method of 3-benzene and dioxolane, it may further comprise the steps:
In the three-necked bottle that has induction stirring, prolong, water trap; Add people's amount of substance ratio and be 1～1.5: 1 aldehyde ketone and pyrocatechol; The catalyst carbon based solid acid of entrainer hexanaphthene and every mol aldehyde ketone consumption 2.0～3.0g, reflux stirs, and water and entrainer hexanaphthene azeotropic that reaction is produced steam; Sampling analysis in the reaction process; Reaction is to the anhydrous water trap 2～5h that gets into again, and stopped reaction, described aldehyde ketone are a kind of in pimelinketone, butanone, acetone, propionic aldehyde, butyraldehyde, isobutyric aldehyde, valeral, isovaleric aldehyde, n-hexyl aldehyde, n-octaldehyde, the phenyl aldehyde.
2. according to claim 11, the compound method of 3-Ben Bing dioxolane is characterized in that: described aldehyde ketone is a pimelinketone.
3. according to claim 11, the compound method of 3-Ben Bing dioxolane is characterized in that: aldehyde ketone is 1.2: 1 with the amount of substance ratio of pyrocatechol.
4. according to claim 11, the compound method of 3-Ben Bing dioxolane is characterized in that: the consumption of catalyst carbon based solid acid is every mol aldehyde ketone consumption 2.5g.
5. according to claim 11, the compound method of 3-Ben Bing dioxolane is characterized in that: reaction gets into 4h in the water trap again to anhydrous.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102846699A CN102766131A (en) | 2012-08-10 | 2012-08-10 | Synthetic method of 1, 3-benzodioxole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102846699A CN102766131A (en) | 2012-08-10 | 2012-08-10 | Synthetic method of 1, 3-benzodioxole |
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| Publication Number | Publication Date |
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| CN102766131A true CN102766131A (en) | 2012-11-07 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CN2012102846699A Pending CN102766131A (en) | 2012-08-10 | 2012-08-10 | Synthetic method of 1, 3-benzodioxole |
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| CN (1) | CN102766131A (en) |
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2012
- 2012-08-10 CN CN2012102846699A patent/CN102766131A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 宋逸婷等: "碳基固体酸催化药物活性中间体苯并二噁茂烷的合成", 《绍兴文理学院学报》 * |
| 郭英雪等: "新型碳基固体酸催化合成缩醛(酮)", 《石油化工》 * |
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Application publication date: 20121107 |