KR101777474B1 - A method for preparing 1,3-prop-1-ene sultone - Google Patents
A method for preparing 1,3-prop-1-ene sultone Download PDFInfo
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- KR101777474B1 KR101777474B1 KR1020150173052A KR20150173052A KR101777474B1 KR 101777474 B1 KR101777474 B1 KR 101777474B1 KR 1020150173052 A KR1020150173052 A KR 1020150173052A KR 20150173052 A KR20150173052 A KR 20150173052A KR 101777474 B1 KR101777474 B1 KR 101777474B1
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- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
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Abstract
The present invention provides a novel process for preparing 1,3-prop-1-enesultone. The production method of the present invention is economical using an inexpensive reagent, and can be produced in a mild condition at a high purity and a high yield, and thus can be easily applied to mass production.
Description
The present invention relates to a process for the production of 1,3-prop-1-enesultone, which is easy and economical to manufacture and which can be mass-produced industrially.
1,3-Propene-1-enesultone (PRS) represented by the following formula (1) is a known compound widely used as an intermediate for pharmaceuticals, an additive for an electrolyte of a lithium ion secondary battery, and the like.
[Chemical Formula 1]
As a method for preparing 1,3-propene-1-enesultone, Chem. Commun. 1997, 611 and Tetrahedron, 1999, 2245 (WH Lee et al.) Synthesized 2-bromo-1,3-propane sultone from allyl bromide via sulfonation, bromination and cyclization, And then, 1,3-prop-1-enesultone is produced through elimination reaction.
According to the above method, 2,3-dibromo-1-propanesulfonate is synthesized to synthesize 1,3-prop-1-ene, and the resultant is cyclized to obtain 2-bromo- Should be synthesized. At this time, in the step of synthesizing and cyclizing 2,3-dibromo-1-propanesulfonate, a reduced pressure of 2 mmHg or less and a temperature of 130 ° C or more are required. In the reaction conditions, 2,3-dibromo- Sulfonate and 2-bromo-1,3-propane sultone are decomposed together, degradation of the yield is intensified. Particularly, as the amount of the reactant increases, the heating condition for a long time is deepened and an oligomer and a polymer substance connected in the form of sulfone ester can be produced together. From this, the desired product, 2-bromo-1,3- The separation becomes more difficult and the overall yield is lowered. Therefore, there is a problem that it is difficult to use the method for mass production.
In Synlett 1998 and 1411, 1,3-dibromo-5,5-dimethylhydantoin was reacted with allylsulfonyl chloride, which was obtained by reacting sodium allylsulfonate with phosphorus oxychloride to give 2-bromo-1,3 -Propane sultone, and then synthesizing the 1,3-prop-1-enesultone by a tribromohydrogenation reaction. However, the synthesis method has a problem that a high amount of 1,3-dibromo-5,5-dimethylhydantoin must be used in a considerable amount, and the yield is low.
Also, Synlett, 2002, 2019 (Peter Metz et al.) Has proposed a ring closing metathesis synthesis from vinyl intermediates, but it is difficult to use industrially because synthesis of vinyl intermediates is not very easy.
In SYNTHESIS No. 10, pp. 1696-1712 (2004), vinyl sulfonyl chloride is reacted with allyl alcohol to form an unsaturated sulfonate, which is then cyclized with a Grubbs ruthenium catalyst to obtain 1,3-prop- A method for producing a sultone is disclosed. However, the above method is difficult to produce vinyl sulfonyl chloride as an intermediate material, and since the price of Grubbs ruthenium catalyst is high, there is a problem in mass production.
Korean Patent Publication No. 2007-0101716 also discloses a process for preparing a halogen-substituted 1,3-propanesultone by a halogenation reaction of 1,3-propanesultone to prepare a halogen-substituted 1,3- And a second step of carrying out halogen hydrogen elimination reaction to the 1,3-propane sultone.
However, in the above method, 3-halogeno-1,3-propanesultone, which is different in halogen substitution position, is produced as a by-product during the halogenation reaction of 1,3-propanesultone, and 3-halogeno-1,3-propane The sultone does not undergo a dehydrohalogenation hydrogenation reaction, and the target 1,3-propanesultone is not produced, so that the yield is not improved.
Korean Patent Laid-Open Publication No. 2009-0045027 discloses a method for producing 1,3-prop-1-enesultone through a chlorination reaction, a cyclization reaction and an elimination reaction as shown in the following reaction formula.
However, the above method is not suitable for commercial production because the reagents used for bromodan, NBS, NCS and the like are expensive.
Accordingly, there is a need for a process for producing 1,3-prop-1-enesultone that is easy to manufacture and is suitable for mass production while eliminating the above problems.
It is an object of the present invention to provide a process for producing 1,3-prop-1-enesultone, which is easy and economical to manufacture and which can be mass-produced industrially.
The present invention provides a novel process for the preparation of 1,3-prop-1-enesultone.
The present invention also provides a process for preparing a compound represented by the formula (2): (S1) a step of preparing a compound represented by the following formula (2) from a compound represented by the following formula (1); (S2) preparing a compound represented by the formula (3) from the compound represented by the formula (2); And (S3) preparing a compound represented by the following general formula (4) from the compound represented by the general formula (3).
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
In Formula 3, Y is -OMs (mesylate ester), -OTs (tosyl acid ester), or -OTf (triflate ester). Preferably, it may be -OMs (mesyl acid ester).
Hereinafter, each step will be described in detail.
(S1): oxidation and cyclization reaction
In the production method of the present invention, the step (S1) is a step of oxidizing the thiol group of the compound of formula (I) and preparing a compound of formula (II) through a cyclization reaction.
The step (S1) may be carried out in the presence of an oxidizing agent capable of oxidizing the thiol group, and preferably hydrogen peroxide (H 2 O 2 ) may be used. However, the present invention is not limited thereto.
In addition, the step (S1) may be carried out in the presence of an acid or phosphorous chloride. As the acid, inorganic acid selected from the group consisting of hydrochloric acid, sulfuric acid and acetic acid can be used, and phosphoryl trichloride (POCl 3 ) can be used as the phosphoryl chloride. Preferably, hydrochloric acid can be used. However, the present invention is not limited thereto.
The step (S1) may be carried out in the presence of an organic solvent commonly used in oxidation and cyclization reactions. Preferably, ethyl acetate, methyl chloride or C1 to C4 alcohols can be used, more preferably methanol. However, the present invention is not limited thereto.
The reaction of step (S1) may be carried out at 25 to 40 占 폚, preferably 30 to 40 占 폚, more preferably 30 to 35 占 폚. However, the present invention is not limited thereto.
(S2) Step: Sulfonic acid esterification reaction
In the preparation process of the present invention, the step (S2) is a step of performing a first purification operation through a sulfonic acid esterification reaction of the compound of formula (2).
The step (S2) may be carried out using a sulfonic acid salt or an anhydrous sulfonic acid used in a conventional sulfonic acid esterification reaction of an alcohol. Preferably, mesyl chloride, tosyl chloride (- ortho, - para), and anhydrous triflic acid can be used. However, the present invention is not limited thereto.
The step (S2) may be carried out using a solvent used for a conventional sulfonic acid esterification reaction of an alcohol. Preferably, toluene, methyl chloride or ethyl acetate can be used. However, the present invention is not limited thereto.
In addition, the step (S2) may be carried out in the presence of a base, especially an organic base. Preferably, triethylamine, di-isopropylethylamine or pyridine can be used, and more preferably triethylamine can be used. However, the present invention is not limited thereto.
The step (S2) may be performed at -10 to 20 ° C, preferably at -5 to 10 ° C, and more preferably at 0 to 5 ° C. However, the present invention is not limited thereto.
Further, according to a preferred embodiment of the present invention, the step (S2) may further comprise a crystallization step.
The solvent used in the crystallization step is preferably water.
(S3) Step: Elimination
In the production method of the present invention, the step (S3) is a step of preparing 1,3-prop-1-enesultone by removing the leaving group (Y) of the compound of formula (3).
The above (S3) reaction can be carried out using a solvent used in a conventional elimination reaction. Preferably, toluene, methyl chloride or ethyl acetate can be used. However, the present invention is not limited thereto.
In addition, the step (S3) may be carried out in the presence of a base, especially an organic base. Preferably, triethylamine, di-isopropylethylamine or pyridine can be used, and more preferably triethylamine can be used. However, the present invention is not limited thereto.
The removal reaction may be carried out at 0 to 30 ° C, preferably at 10 to 30 ° C, more preferably at 20 to 30 ° C. However, the present invention is not limited thereto.
Further, according to a preferred embodiment of the present invention, the step (S3) may further comprise a crystallization step. The solvent used in the crystallization step is preferably isopropanol or ethanol. More preferably, isopropanol can be used. However, the present invention is not limited thereto.
The production process of the present invention can produce the existing 1,3-prop-1-enolsultone at a low price by using an inexpensive raw material, and the reaction process is simple and mild, and thus, it is very suitable for mass production.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.
In addition, the reagents and solvents mentioned below were purchased from Sigma-Aldrich Korea unless otherwise noted, and 1 H NMR was measured using a Oxford NMR 300 MHz Spectrometer from Varian Mercury Instrument (Varian Mercury).
Example 1
Step 1: Preparation of prop-2-ol-1,3-sultone
Hydrogen peroxide (35%) (269 g, 2.77 mmol) was added at room temperature to a stirred solution of alpha-thioglycerol (100 g, 0.92 mol) in 500 ml of methanol, Kept at 30 to 40 ° C and slowly dropped. After completion of the dropwise addition, the reaction was continued while maintaining the internal temperature at 30 to 40 ° C. When the reaction was completed, the reaction mixture was concentrated under reduced pressure to remove the solvent, and then diluted with 300 ml of ethyl acetate. Sodium sulfite (233 g, 1.85 mol) and sodium sulfate (50 g) were added to the diluted reaction solution, and the filtrate was concentrated to obtain 127.7 g (yield: 100%) of prop-2-ol-1,3- .
1 H-NMR (DMSO, 300MHz ): δ (ppm) 3.24 ~ 3.32 (m, 1H), 3.63 ~ 3.69 (m, 1H), 4.25 ~ 4.28 (m, 1H), 4.50 ~ 4.53 (m 1H.), 4.73-4.76 (m, 1H), 5.70-6.10 (b, 1H)
Step 2-1: Preparation of prop-2-ol-1,3-sulphonemethanesulfonate
The prop-2-ol-1,3-sultone (127.7 g, 0.92 mol) prepared in Step 1 was dissolved in 639 ml of ethyl acetate while cooling the internal temperature to 0-5 ° C, (MsCl) (105 g, 0.92 mol). Then triethylamine (93 g, 0.92 mol) was slowly added dropwise maintaining the internal temperature. After completion of the dropwise addition, 639 ml of purified water was added thereto, followed by stirring and filtration. The filtered crystals were washed with purified water and vacuum dried at an internal temperature of 50 ° C to obtain 89.5 g (yield: 45.0%) of prop-2-ol-1,3-sulphonemethanesulfonate.
1 H-NMR (CDCl 3, 300MHz): δ (ppm) 3.33 (s, 3H), 3.86 ~ 3.98 (m, 2H), 4.67 ~ 4.76 (m, 2 H), 5.71 ~ 5.75 (m, 1H)
Step 2-2: Preparation of prop-2-ol-1,3-sulphate tosylate
114.3 g (Yield: 42.5%) of the title compound was obtained by the same procedure as in the step 2-1 except that tosyl chloride (175 g, 0.92 mol) was used instead of methyl chloride.
1 H-NMR (CDCl 3, 300MHz): δ (ppm) 2.34 (s, 3H), 3.46 (m, 2H), 4.54 (m, 2H), 5.74 (m, 1 H), 7.46 (m, 2H) , ≪ / RTI > 7.75 (m, 2H)
Step 2-3: Preparation of prop-2-ol-1,3-
(Yield: 41.0%) of the title compound was obtained in the same manners as in the step 2-1, except that anhydrous triflic acid (260 g, 0.92 mol) was used instead of the methyl chloride chloride.
1 H-NMR (CDCl 3, 300MHz): δ (ppm) 3.21 ~ 3.46 (m, 2H), 4.29 ~ 4.54 (m, 2H), 5.74 (m, 1H)
Step 3: Preparation of 1,3-prop-1-enesultone
Prop-2-ol-1,3-sulphonemethanesulfonate (89.5 g, 0.41 mol) prepared in Step 2-1 was dissolved in 297 ml of ethyl acetate and stirred. While the internal temperature was maintained at 20 to 30 ° C, Ethylamine (50 g, 0.49 mol) was slowly added dropwise. After completion of dropwise addition, the mixture was stirred for 1 hour while maintaining the internal temperature at the same temperature. After confirming the termination of the reaction, the reaction solution was adjusted to pH 1 to 2 using an aqueous solution of hydrogen chloride (1 M), and the organic layer was separated by layer separation. 65 g of sodium sulfate was added to the separated organic layer, dried and filtered, and the filtrate was concentrated. 447 ml of isopropanol was added to the concentrated residue, stirred at an internal temperature of 20 to 25 ° C for 1 hour and filtered. The filtered crystals were dried under vacuum at an internal temperature of 50 DEG C or lower to obtain 36.9 g (yield: 75.0%, purity: 99.9% or more) of 1,3-prop-1-enesultone.
1 H-NMR (DMSO, d 6): δ (ppm) 5.11 ~ 5.12 (m, 1H), 6.81 ~ 6.82 (m, 1H), 7.02 ~ 7.04 (m, 1H)
Claims (12)
(S2) preparing a compound represented by the formula (3) from the compound represented by the formula (2); And
(S3) preparing a compound represented by the following formula (4) from the compound represented by the formula (3);
(S1) is carried out in the presence of an oxidizing agent, wherein the step (S1) is carried out in the presence of an oxidizing agent.
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
In Formula 3, Y is -OMs (mesylate ester), -OTs (tosyl acid ester), or -OTf (triflate ester).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11180469B2 (en) * | 2018-06-27 | 2021-11-23 | Samhwa Paints Industries Co., Ltd. | Method for preparing sultone derivatives |
| WO2022065796A1 (en) | 2020-09-28 | 2022-03-31 | 주식회사 엘지에너지솔루션 | Additive for nonaqueous electrolytic solution, nonaqueous electrolytic solution containing same, and lithium secondary battery |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111233823B (en) * | 2018-11-29 | 2022-05-17 | 张家港市国泰华荣化工新材料有限公司 | Synthesis method of 2-fluoro-1, 3-propane sultone |
| KR20230058778A (en) | 2021-10-25 | 2023-05-03 | 엘티소재주식회사 | Method for preparing 1,3-propanesultone derivatives |
| KR20230108133A (en) * | 2022-01-10 | 2023-07-18 | 주식회사 엘지화학 | Manufacturing method of cyclic sulfonic acid ester derivative compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101456856A (en) | 2009-01-07 | 2009-06-17 | 石家庄圣泰化工有限公司 | Preparation method of 1-propylene-1, 3-sultone |
| US20140329746A1 (en) | 2004-12-22 | 2014-11-06 | Xianqi Kong | Methods and compositions for treating amyloid-related diseases |
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| US20140329746A1 (en) | 2004-12-22 | 2014-11-06 | Xianqi Kong | Methods and compositions for treating amyloid-related diseases |
| CN101456856A (en) | 2009-01-07 | 2009-06-17 | 石家庄圣泰化工有限公司 | Preparation method of 1-propylene-1, 3-sultone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11180469B2 (en) * | 2018-06-27 | 2021-11-23 | Samhwa Paints Industries Co., Ltd. | Method for preparing sultone derivatives |
| WO2022065796A1 (en) | 2020-09-28 | 2022-03-31 | 주식회사 엘지에너지솔루션 | Additive for nonaqueous electrolytic solution, nonaqueous electrolytic solution containing same, and lithium secondary battery |
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