CN102659645A - Method for synthesizing ethylmethane sulfonate - Google Patents
Method for synthesizing ethylmethane sulfonate Download PDFInfo
- Publication number
- CN102659645A CN102659645A CN2012101375142A CN201210137514A CN102659645A CN 102659645 A CN102659645 A CN 102659645A CN 2012101375142 A CN2012101375142 A CN 2012101375142A CN 201210137514 A CN201210137514 A CN 201210137514A CN 102659645 A CN102659645 A CN 102659645A
- Authority
- CN
- China
- Prior art keywords
- triethyl orthoformate
- ethylmethane sulfonate
- purity
- methanesulfonic
- cut
- 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
Images
Abstract
The invention discloses a method for synthesizing ethylmethane sulfonate. The synthetic method comprises the following steps of reacting methanesulfonic acid with triethyl orthoformate, wherein the methanesulfonic acid and the triethyl orthoformate serve as raw materials; performing atmospheric distillation to separate by-products, namely ethyl formate and ethanol; distilling under reduced pressure to separate excessive triethyl orthoformate, and recycling the separated triethyl orthoformate; adding ethanol, performing azeotropic distillation under normal pressure to remove the residual triethyl orthoformate; and distilling under reduced pressure to obtain ethylmethane sulfonate with a purity of over 99.5 percent. The method is low in cost, easy to operate, high in efficiency and high in yield; moreover, wastes are recycled; and the method has actual significance and high application value for the industrial research on the production methods for high-purity ethylmethane sulfonate.
Description
Technical field
The present invention relates to the ethylmethane sulfonate technology of preparing, more particularly, relate to a kind of compound method of ethylmethane sulfonate.
Background technology
Ethylmethane sulfonate generally carries out acetylize by methanesulfonic and gets.Because it can suddenly change by modificator gene, is widely used in cancer research, and as the biological induced-mutation agent; Compare with other mutagenic compound, the point mutation frequency that ethylmethane sulfonate mutation produces is high, and is mostly recessive mutation, and chromosome aberration is less relatively, need not carry out genetic transformation, thereby is used for making up mutant library widely.
Because sulfonic acid and alcohol can not directly carry out esterification, ethylmethane sulfonate can only be made by the indirect esterification of methylsulphonic acid.Bibliographical information is arranged, and sulfonic acid can be converted into corresponding ester with alcohol smoothly under the effect of 2.5 normal trimethylchlorosilanes; Or sulfonic acid used chlorocarbonate, and alkyl one chlorine sulfoxide, positive borine or dialkyl sulphoxide are handled, and can prepare corresponding ester; This class methods expensive raw materials, productive rate is not high, complex operation, using value is little.Another kind method is that the interesterification through sulfonic acid and carboxylicesters prepares sulphonate.Have document to show, can carry out esterification synthesizing methyl sulfonic acid ethyl ester, but because its lower productive rate has limited its application through methylsulphonic acid and diethyl carbonate.
Summary of the invention
To the above-mentioned shortcoming that exists in the prior art, the purpose of this invention is to provide a kind of compound method of ethylmethane sulfonate, at short notice the ethylmethane sulfonate of synthesis of high purity.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
The compound method of this ethylmethane sulfonate is for being that raw material reacts with the erucic acid raw material with methanesulfonic and triethyl orthoformate, and sub product ethyl formate and ethanol are isolated in first then air distillation respectively; Excess raw material triethyl orthoformate and recovery are isolated in underpressure distillation again; Add ethanol normal pressure component distillation again, remove remaining triethyl orthoformate; It is the methanesulfonic ethyl ester more than 99.5% that last underpressure distillation gets purity.
The purity of described methanesulfonic raw material is 98%;
The purity of described triethyl orthoformate raw material is 99%;
Described methanesulfonic is 1: 1.4～1: 4 with the reaction mass ratio of triethyl orthoformate.
Described reactive mode is for being added drop-wise to methanesulfonic in the triethyl orthoformate and stirring, and the dropping time is 1～2 hour.
Described reaction conditions is backflow, and return time is 2.5～3.5 hours.
It is 1 that described component distillation needs the mass ratio of the theoretical yield of consumption of ethanol and ethylmethane sulfonate: 1.5-1: 2.5.
In technique scheme, the compound method of ethylmethane sulfonate of the present invention is that raw material reacts with methanesulfonic and triethyl orthoformate, and sub product ethyl formate and ethanol are isolated in first then air distillation respectively; Excess raw material triethyl orthoformate and recovery are isolated in underpressure distillation again; Add ethanol normal pressure component distillation again, remove remaining triethyl orthoformate; It is the methanesulfonic ethyl ester more than 99.5% that last underpressure distillation gets purity.This compound method cost is low, simple to operation, and efficient is high, and productive rate is high, and waste material can reuse, and the research in industry has practical significance and using value very much to high-purity methanesulfonic acid ethyl ester working method.
Description of drawings
Fig. 1 is the generated data table of embodiments of the invention 1～7;
Fig. 2 is the generated data table of embodiments of the invention 8～9;
Fig. 3 is the generated data table of embodiments of the invention 10.
Embodiment
Further specify technical scheme of the present invention below in conjunction with accompanying drawing and embodiment.
See also Fig. 1～shown in Figure 3:
Embodiment 1:
206.4g methanesulfonic is added drop-wise in the 500ml triethyl orthoformate, heated and stirred, and solution temperature is controlled at about 80 ℃, drips about 1.5h to finish, and drips to finish back backflow 3h; The cut of 52 ℃ and 76 ℃ is collected in air distillation respectively; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 250Pa, do not have cut before 50 ℃, and the cut when collecting 64 ℃ is the methanesulfonic ethyl ester, detect, and purity is 99.624% (GC), 62.6g altogether, and yield is 23.5%.
Embodiment 2:
172.1g methanesulfonic is added drop-wise in the 500ml triethyl orthoformate, heated and stirred, and solution temperature is controlled at about 80 ℃, drips about 1.5h to finish, and drips to finish back backflow 3h; Air distillation, the cut when collecting 52 ℃ and 69 ℃ of left and right sides respectively; + 100ml absolute ethyl alcohol (A.R), air distillation, 75-66 ℃ has cut, collects; After air distillation finishes, cooling, underpressure distillation, vacuum tightness is 400Pa, and the cut when collecting 81 ℃ detects, and purity is 99.537% (GC), is total to 104g, and yield is 46.8%.
Embodiment 3:
144.7g methanesulfonic is added drop-wise in the 500ml triethyl orthoformate, heated and stirred, and solution temperature is controlled at about 80 ℃, drips about 1.5h to finish, and drips to finish back backflow 3h; The cut of 49 ℃ and 68 ℃ is collected in air distillation respectively; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 50Pa, and 34 ℃ have cut, collect, and purity is 98.54% (GC), directly reclaim; + 100ml absolute ethyl alcohol (A.R), air distillation, 76-66 ℃ has cut, collects; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 40Pa, collect 46 ℃ cut, detect, and purity is 99.796% (GC), and qualified is 122.6g, and productive rate is 65.6%.
Embodiment 4:
128.1g methanesulfonic is added drop-wise in the 500ml triethyl orthoformate, heated and stirred, and solution temperature is controlled at about 80 ℃, drips 1.5h and finishes, and drips to finish back backflow 3h; The cut of 49 ℃ and 68 ℃ is collected in air distillation respectively; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 160Pa, and 46 ℃ have cut, collect, and, purity is 99.01% (GC), reclaims; + 100ml absolute ethyl alcohol (A.R), air distillation, 76-66 ℃ has cut, collects; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 180Pa, collect 56 ℃ cut, detect, and purity is 99.525% (GC), and qualified is 134.7g, productive rate 81.4%.
Embodiment 5:
112.1g methanesulfonic is added drop-wise in the 500ml triethyl orthoformate, heated and stirred, and solution temperature is controlled at about 80 ℃, drips 1.5h and finishes, and drips to finish back backflow 3h; The cut of 53 ℃ and 68 ℃ is collected in air distillation respectively; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 100Pa, and 44 ℃ have cut, collect, and, purity is 98.89% (GC), reclaims; + 60ml absolute ethyl alcohol (A.R), air distillation, 76-66 ℃ has cut, collects; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 120Pa, collect 54 ℃ cut, detect, and purity is 99.778% (GC), and qualified is 118.9g, productive rate 82.1%.
Embodiment 6:
96.2g methanesulfonic is added drop-wise in the 500ml triethyl orthoformate, heated and stirred, and solution temperature is controlled at about 80 ℃, drips 1.5h and finishes, and drips to finish back backflow 3h; The cut of 54 ℃ and 66 ℃ is collected in air distillation respectively; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 220Pa, and 47 ℃ have cut, collect, and purity is 99.11% (GC), reclaim; + 60ml absolute ethyl alcohol (A.R), air distillation, 76-66 ℃ has cut, collects; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 200Pa, collect 61 ℃ cut, detect, and purity is 99.513% (GC), and qualified is 107.8g, productive rate 84.3%.
Embodiment 7:
72.2g methanesulfonic is added drop-wise in the 500ml triethyl orthoformate, heated and stirred, and solution temperature is controlled at about 80 ℃, drips 1.5h and finishes, and drips to finish back backflow 3h; The cut of 54 ℃ and 66 ℃ is collected in air distillation respectively; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 120Pa, and 44 ℃ have cut, collect, and, purity is 98.94% (GC), reclaims; + 60ml absolute ethyl alcohol (A.R), air distillation, 76-66 ℃ has cut, collects; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 150Pa, collect 56 ℃ cut, detect, and purity is 99.622% (GC), and qualified is 79.6g, productive rate 85.2%.
Embodiment 8:
128.6g methanesulfonic is added drop-wise in the 500ml triethyl orthoformate, heated and stirred, and solution temperature is controlled at about 80 ℃, drips 1h and finishes, and drips to finish back backflow 1.5h; The cut of 54 ℃ and 66 ℃ is collected in air distillation respectively; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 240Pa, and 48 ℃ have cut, collect, and purity is 99.23% (GC), reclaim; + 100ml absolute ethyl alcohol (A.R), air distillation, 76-66 ℃ has cut, collects; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 220Pa, collect 61 ℃ cut, detect, and purity is 99.617% (GC), and qualified is 120.2g, productive rate 72.4%.
Embodiment 9:
129.3g methanesulfonic is added drop-wise in the 500ml triethyl orthoformate, heated and stirred, and solution temperature is controlled at about 80 ℃, drips 2h and finishes, and drips to finish back backflow 4.5h; The cut of 54 ℃ and 66 ℃ is collected in air distillation respectively; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 180Pa, and 46 ℃ have cut, collect, and purity is 99.08% (GC), reclaim; + 100ml absolute ethyl alcohol (A.R), air distillation, 76-66 ℃ has cut, collects; Underpressure distillation behind the no cut below 90 ℃, vacuum tightness are 210Pa, collect 59 ℃ cut, detect, and purity is 99.586% (GC), and qualified is 133.8g, productive rate 80.1%.
Embodiment 10:
126.7g methanesulfonic is added drop-wise in the 500ml triethyl orthoformate, heated and stirred, and solution temperature is controlled at about 80 ℃, drips 1.5h and finishes, and drips to finish back backflow 3h; Distillation, 52 ℃ have cut, collect; About 67 ℃ cut is arranged, collect; 145 ℃ have fraction collection, are excessive triethyl orthoformate, and purity is 82.72% (GC); Collect front-end volatiles and 200 ℃ respectively, detect respectively, purity is 55.018% (GC) and 99.183% (GC), and qualified is 111.3g, and productive rate is 67.9%.
Those of ordinary skill in the art will be appreciated that; Above embodiment is used for explaining the present invention; And be not to be used as qualification of the present invention; As long as in connotation scope of the present invention, all will drop in claims scope of the present invention variation, the modification of the above embodiment.
Claims (5)
1. the compound method of an ethylmethane sulfonate is characterized in that:
With methanesulfonic and triethyl orthoformate is that raw material reacts, and sub product ethyl formate and ethanol are isolated in first then air distillation respectively; Excess raw material triethyl orthoformate and recovery are isolated in underpressure distillation again; Add ethanol normal pressure component distillation again, remove remaining triethyl orthoformate; It is the methanesulfonic ethyl ester more than 99.5% that last underpressure distillation gets purity.
2. the compound method of ethylmethane sulfonate as claimed in claim 1 is characterized in that:
The purity of described methanesulfonic raw material is 98%;
The purity of described triethyl orthoformate raw material is 99%;
Described methanesulfonic is 1: 1.4～1: 4 with the reaction mass ratio of triethyl orthoformate.
3. according to claim 1 or claim 2 the compound method of ethylmethane sulfonate is characterized in that:
Described reactive mode is for being added drop-wise to methanesulfonic in the triethyl orthoformate and stirring, and the dropping time is 1～2 hour.
4. the compound method of ethylmethane sulfonate as claimed in claim 3 is characterized in that:
Described reaction conditions is backflow, and return time is 2.5～3.5 hours.
5. the compound method of ethylmethane sulfonate as claimed in claim 1 is characterized in that:
It is 1 that described component distillation needs the mass ratio of the theoretical yield of consumption of ethanol and ethylmethane sulfonate: 1.5-1: 2.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101375142A CN102659645A (en) | 2012-05-04 | 2012-05-04 | Method for synthesizing ethylmethane sulfonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101375142A CN102659645A (en) | 2012-05-04 | 2012-05-04 | Method for synthesizing ethylmethane sulfonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102659645A true CN102659645A (en) | 2012-09-12 |
Family
ID=46769258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101375142A Pending CN102659645A (en) | 2012-05-04 | 2012-05-04 | Method for synthesizing ethylmethane sulfonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102659645A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2928859A (en) * | 1958-06-23 | 1960-03-15 | Chemstrand Corp | Alkylation of acids with alkyl orthocarboxylates |
-
2012
- 2012-05-04 CN CN2012101375142A patent/CN102659645A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2928859A (en) * | 1958-06-23 | 1960-03-15 | Chemstrand Corp | Alkylation of acids with alkyl orthocarboxylates |
Non-Patent Citations (1)
| Title |
|---|
| A.A.PADMAPRIYA,ET AL: "A new method for the esterification of sulphonic acids", 《SYNTHETIC COMMUNICATIONS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101921175B (en) | Process for producing an organic compound | |
| CN109516971B (en) | Synthesis method of battery-grade vinyl sulfate | |
| EP2602250B1 (en) | Method for preparing rosuvastatin calcium intermediate | |
| CN107176929B (en) | Method for preparing 1H-tebuconazole | |
| CN102659645A (en) | Method for synthesizing ethylmethane sulfonate | |
| CN101421223B (en) | Process for producing (meth)acrylic ester | |
| US10294189B2 (en) | Process for producing fluorinated electrolyte solvent | |
| CN1279178C (en) | Process for prepn. of substituted carboxylic esters | |
| CN102199127A (en) | Method for preparing azoxystrobin | |
| CN111072630A (en) | Preparation method and application of bromopyrazole compound intermediate | |
| CN105968004A (en) | Method for completely continuously producing methyl ethyl carbonate co-produced diethyl carbonate | |
| CN101357908B (en) | Bisbenzothiazole disulfide and triphenylphosphine preparation by means of one pot | |
| CN105294758A (en) | Phosphite antioxidant and preparation method thereof | |
| CN106831493A (en) | The synthetic method of tetrabutyl urea | |
| CN103588842A (en) | Synthetic method of betamethasone or prednisolone intermediate | |
| CN103012461B (en) | Preparation method of biotin key intermediate 1, 2-bi(trimethylsilanolate) cyclohexene | |
| CN106748695B (en) | Preparation method of m-trifluoromethyl cinnamaldehyde | |
| AU666729B2 (en) | Process for preparing tetronic acid alkyl esters | |
| JP6046257B2 (en) | Method for producing trifluoromethyl group-containing cyclic carbonate | |
| CN106674121A (en) | Preparation method of 4-halogen-1H-imidazole | |
| CN202626061U (en) | Synthesizing device of ethylmethane sulfonate | |
| CN103709032A (en) | Preparation method of dibutyl carbonate through catalyzed synthesis of proline ionic liquid | |
| CN113121321B (en) | Recovery and reuse method of a-R alkoxy p-chlorobenzyl phosphate monoester | |
| CN101607871A (en) | Method for preparing 4, 4' -dimethylolbiphenyl | |
| CN103183592A (en) | Preparation method of 2-chloro-1,1,1-trialkoxy ethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| CB02 | Change of applicant information |
Address after: 201406 Fengxian District, South Lake Town, Hong Kong Road, No. 1008, No. Applicant after: ALADDIN INDUSTRIAL CORPORATION Address before: 201406 Fengxian District, South Lake Town, Hong Kong Road, No. 1008, No. Applicant before: Shanghai Jingchun Scientific Company Limited |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: SHANGHAI JINGCHUN INDUSTRIAL CO.,LTD. TO: SHANGHAI JINGCHUN BIOCHEMICAL TECHNOLOGY CO., LTD. |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120912 |