CN104151285A - Method for preparing 3,4-methylenedioxy mandelic acid - Google Patents
Method for preparing 3,4-methylenedioxy mandelic acid Download PDFInfo
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- CN104151285A CN104151285A CN201410399777.XA CN201410399777A CN104151285A CN 104151285 A CN104151285 A CN 104151285A CN 201410399777 A CN201410399777 A CN 201410399777A CN 104151285 A CN104151285 A CN 104151285A
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- acid
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- methylenedioxy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
- C07D317/60—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 3,4-methylenedioxy mandelic acid. A key point of the invention is that under the condition of the existence of sulfuric acid with a concentration higher than 96%, when 1,2-methylenedioxybenzene and glyoxylic acid are subjected to a reaction for preparing 3,4-methylenedioxy mandelic acid, acetic anhydride is added for diluting during the reaction. When acetic anhydride is added for diluting, the reaction time of 3,4-methylenedioxy mandelic acid and glyoxylic acid, 1,2-methylenedioxybenzene conversion rate, 3,4-methylenedioxy mandelic acid selectivity, 3,4-methylenedioxy mandelic acid yield and stirring convenience are greatly improved. Also, the method has the advantages of mild reaction conditions, no special requirement on equipment, and good industrial application prospect.
Description
Technical field
The present invention relates to chemical industry and manufacture field.Relate in particular to a kind of method of preparing MDMA.
Background technology
In prior art, under the condition existing at strong acid such as sulfuric acid or phosphoric acid, make 1,2-methylenedioxybenzenes and glyoxalic acid reaction prepare 3, the method of 4-methylenedioxy-mandelic acid (for example, JP 54-95573 communique, Perfumer & Flavourist, 14,13 (1989)), and in WO01/27100 (2001) (Patents CN1379770A), be reported in and in reaction system, add solvent can overcome in reaction process reaction solution high viscosity or solidify and stir the problem that becomes very difficult.At this moment can select different non-proton organic solvents if ether, diisopropyl ether, dibutyl ether, tetrahydrofuran (THF), acetone, 2-butanone, 2 pentanone, ethyl formate, ethyl acetate, isopropyl acetate, butylacetate, dimethyl formamide, 1-methyl-2-are than pyrrolidone, methylcarbonate, diethyl carbonate, methyl-sulphoxide etc.
These aprotic organic solvents or flash-point are low, or high potential safety hazard or the economic short slab of existing of price.Another method is to use organic acid in reaction, and if formic acid, acetic acid, propionic acid, trifluoroacetic acid etc. are solvent, the toxicity price large, that have that these organic acids have is high, therefore be preferably use acetic acid.And the zero pour of acetic acid is 16.7 ℃, in low temperature environment, use limitedly, for this reason, not yet there is a kind of more rational preparation method to make public.
Summary of the invention
The object of the present invention is to provide a kind ofly at suitable temperature condition, to make 1,2-methylenedioxybenzenes and glyoxalic acid reaction high conversion, high yield, be applicable to the preparation method of the MDMA of suitability for industrialized production.It is characterized in that, under more than 96% sulfuric acid existence condition, when 1,2-methylenedioxybenzenes and glyoxalic acid reaction are prepared MDMA, add diacetyl oxide dilution to react.
Reaction formula is as follows:
Embodiment
As the strong acid using in the present invention's reaction, be the inorganic acids such as sulfuric acid, phosphoric acid: preferably use sulfuric acid.In addition, preferably use more than 96% sulfuric acid.Its usage quantity is with respect to the mol ratio of 1 mole of 1.2-methylenedioxybenzenes, preferably 2.05 moles.
The oxoethanoic acid using in reaction of the present invention is more than 40% aqueous solution.Its usage quantity is 0.9～2 mole with respect to the mol ratio of 1,2-methylenedioxybenzenes, is preferably 1.1 moles.
In reaction of the present invention with respect to 1kg1, the usage quantity of the thinner diacetyl oxide that 2-methylenedioxybenzenes is used, preferably 50ml (54g)-1000ml (1080g), more preferably 100ml (108g)～400ml (432g).If usage quantity is less than 50ml, the DeGrain of dilution, stirs, conducts heat and be all more difficult, and the selection rate of object product, productive rate reduce.On the other hand, if during more than 1000ml, occur that the rarer speed of response of reaction solution is slow, long reaction time, the problem that the selection rate of object product lowers simultaneously, curing problem while using in addition diacetyl oxide to replace acetic acid to avoid low temperature environment operation, and make to stir, heat transfer process has greatly improved.
Reaction of the present invention by dripping the mixture of oxoethanoic acid and sulfuric acid in the mixed solution of 1,2-methylenedioxybenzenes and diacetyl oxide, and temperature of reaction is now-20～30 ℃, is preferably 0 ℃.In reaction process, do not need not produce pressure yet.Reaction times is generally 1～20 hour, preferably 1～10 hour.The reaction product obtaining can add appropriate water dilution crystallization, and then direct filtration obtains MDMA product.
Embodiment 1
In 500ml four-hole boiling flask, add 1, then 2-methylenedioxybenzenes 50.0g (0.409mol) and diacetyl oxide 16.52ml (being equivalent to acetic acid 20ml) (diacetyl oxide is 330.4ml/kg with respect to the usage quantity of 1,2-methylenedioxybenzenes) while stir and be cooled to 0 ℃.Then drip the mixed solution of 83.4g (0.45mol) 40% oxoethanoic acid and 85.8g (0.839mol) 96% sulfuric acid, then stir 5h at 0 ℃, whole process stirs carries out smoothly.
Aftertreatment: slowly drip 102.0g (1.68m.l) 28% ammoniacal liquor and neutralize, then add 2-butanone 100ml, be heated to 60 ℃, the MDMA of generation is extracted in organic phase.Use high-efficient liquid phase chromatogram technique analysis organic layer, result is: the transformation efficiency of 1,2-methylenedioxybenzenes is 97%, and the selection rate of MDMA is 94%, and productive rate is 91.2%.
Embodiment 2～7
Except changing diacetyl oxide for the usage quantity of 1,2-methylenedioxybenzenes with outside the reaction times in embodiment 1, other condition is identical with embodiment 1.Result is as shown in table 1:
Note: the amount of diacetyl oxide be diacetyl oxide with respect to 1Kg1, the usage quantity of 2-methylenedioxybenzenes
Comparative example 1
Except the diacetyl oxide in embodiment 1 is replaced with acetic acid, other reacting similarly to Example 1.As a result 1, the transformation efficiency of 2-methylenedioxybenzenes is 93%, and the selection rate of MDMA is 89%, and productive rate is 83%.
Comparative example 1～3
Except changing in comparative example 1 with respect to 1Kg1, the acetic acid amount that 2 one methylenedioxybenzenes are used and outside the reaction times, other condition is identical with comparative example 1.Result is as shown in table 2.
Note: acetic acid amount be acetic acid with respect to 1Kg1, the usage quantity of 2-methylenedioxybenzenes.
Conclusion: by above 2 table contrasts, we can find out: while using diacetyl oxide to dilute, 3, the reaction times of 4-methylenedioxy-mandelic acid and oxoethanoic acid, 1, the transformation efficiency of 2-methylenedioxybenzenes, MDMA selection rate, MDMA productive rate and and the complexity that stirs all have preferably and improve, simultaneous reactions mild condition, equipment has wide industrial applications prospect without particular requirement.
Claims (6)
1. a method of preparing MDMA, is characterized in that: under 96% above sulfuric acid existence condition, when 1,2-methylenedioxybenzenes and glyoxalic acid reaction are prepared MDMA, add second dilution to react.
2. a kind of method of preparing MDMA according to claim 1, is characterized in that, the usage quantity of 96% above sulfuric acid is 2.05 moles with respect to the mol ratio of 1,2-methylenedioxybenzenes.
3. a kind of method of preparing MDMA according to claim 1, is characterized in that, oxoethanoic acid usage quantity is 1.1 moles with respect to the mol ratio of 1,2-methylenedioxybenzenes.
4. a kind of method of preparing MDMA according to claim 1, is characterized in that, diacetyl oxide usage quantity is with respect to 1kg1, and the usage quantity of 2-methylenedioxybenzenes is 50ml (54g)-1000ml (1080g).
5. according to a kind of method of preparing MDMA described in claim 1-4, it is characterized in that, reaction is carried out at the temperature of-20～-30～C.
6. according to the method for preparing MDMA described in claim 1-4, it is characterized in that, the reaction times is 1-20 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410399777.XA CN104151285A (en) | 2014-08-14 | 2014-08-14 | Method for preparing 3,4-methylenedioxy mandelic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410399777.XA CN104151285A (en) | 2014-08-14 | 2014-08-14 | Method for preparing 3,4-methylenedioxy mandelic acid |
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| CN104151285A true CN104151285A (en) | 2014-11-19 |
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| CN201410399777.XA Pending CN104151285A (en) | 2014-08-14 | 2014-08-14 | Method for preparing 3,4-methylenedioxy mandelic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837552A (en) * | 2016-04-01 | 2016-08-10 | 衢州信步化工科技有限公司 | Treating method for synthesis reaction solution used for intermediate of heliotropin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002114774A (en) * | 2000-10-04 | 2002-04-16 | Ube Ind Ltd | Method of producing 3,4-methylene-dioxymandelic acid |
| CN1379770A (en) * | 1999-10-13 | 2002-11-13 | 宇部兴产株式会社 | Process for preparation of 3,4-methylenedioxy-mandelic acid |
| CN1400972A (en) * | 2000-02-02 | 2003-03-05 | 宇部兴产株式会社 | Process for preparing piperonal |
| CN103724316A (en) * | 2013-12-20 | 2014-04-16 | 暨南大学 | Preparation method and application of sesamol intermediate heliotropin |
-
2014
- 2014-08-14 CN CN201410399777.XA patent/CN104151285A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379770A (en) * | 1999-10-13 | 2002-11-13 | 宇部兴产株式会社 | Process for preparation of 3,4-methylenedioxy-mandelic acid |
| CN1400972A (en) * | 2000-02-02 | 2003-03-05 | 宇部兴产株式会社 | Process for preparing piperonal |
| JP2002114774A (en) * | 2000-10-04 | 2002-04-16 | Ube Ind Ltd | Method of producing 3,4-methylene-dioxymandelic acid |
| CN103724316A (en) * | 2013-12-20 | 2014-04-16 | 暨南大学 | Preparation method and application of sesamol intermediate heliotropin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837552A (en) * | 2016-04-01 | 2016-08-10 | 衢州信步化工科技有限公司 | Treating method for synthesis reaction solution used for intermediate of heliotropin |
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Application publication date: 20141119 |