CN109748892B - Preparation method of 3-halogenated tetrahydrofuran - Google Patents
Preparation method of 3-halogenated tetrahydrofuran Download PDFInfo
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Abstract
The invention discloses a preparation method of 3-halogenated tetrahydrofuran. The method comprises the following steps: reacting a compound shown in a formula I with a reducing agent in an organic solvent at the temperature of 0-85 ℃ to obtain the compound; wherein R is 1 And R 2 The same, are all selected from chlorine or bromine; the reducing agent is sodium borohydride or potassium borohydride; the organic solvent is ethylene glycol dimethyl ether, 2-chloroethyl methyl ether, diethyl ether, tetrahydrofuran or methyl tetrahydrofuran. The method has the advantages of few reaction steps, simple process, low raw material cost, less equipment investment and superior product price, and the product yield can reach 80-95 percent; in addition, the method has little pollution and is environment-friendly and suitable for large-scale industrial production.
Description
Technical Field
The invention relates to a preparation method of 3-halogenated tetrahydrofuran.
Background
The 3-halogenated tetrahydrofuran is a common intermediate for synthesizing pesticides and medicines, wherein the 3-chlorotetrahydrofuran is a key raw material for preparing insecticide dinotefuran, and the prior art discloses few preparation methods of the 3-halogenated tetrahydrofuran, because 2-position of the tetrahydrofuran is easier to be substituted, and 3-position substitution is relatively difficult.
The existing methods for synthesizing 3-halogenated tetrahydrofuran mainly comprise the following methods:
1.β-Halo ether synthesis of olefinic alcohols:stereochemistry and conformation of 2-substituted 3-halotetrahydropyran and-furan precursors.Crombie,Leslie and Wyvill,Robert D.Journal of the Chemical Society,Perkin Transactions 1:Organic and Bio-Organic Chemistry(1972-1999),(9),1971-8；1985.
this document uses tetrahydrofuran as starting material and firstly halogenates it to give 2, 3-dihalotetrahydrofuran and secondly dechlorinates it with lithium aluminium hydride to give 3-halogenated tetrahydrofuran in 75% yield, but the reducing agent lithium aluminium hydride is expensive and has no competitive advantage.
2.Synthesis of some olefinic acids with tetrahydro-β-halofuran and-pyran derivatives as intermediates.Ansell.M.F.and Brown.S.S.Journal of the Chemical Society,1788-95；1957
The document takes 2, 3-dichlorofuran as a raw material, and 3-chlorotetrahydrofuran is obtained by reducing with lithium aluminum hydride, so that the yield is 81 percent, the cost is high, and the method is not suitable for industrial production.
3. Using gamma-butyrolactone as a raw material and elemental halogen as a raw material, firstly synthesizing 3-halogenated-gamma-butyrolactone, then reducing the 3-halogenated-gamma-butyrolactone by using a reducing agent to obtain 2-halogenated-1, 4-butanediol, and then carrying out ring closure under the action of a dehydrating agent to obtain the 3-halogenated tetrahydrofuran.
Chinese patent application CN106749116A discloses the following methods:
the method has the advantages of relatively cheap raw materials, more synthesis steps, low yield, high cost and unsuitability for industrial production, and impurities are easily generated by ring opening in the halogenation reaction process.
Therefore, there is a great need in the art to develop a novel method for preparing 3-halogenated tetrahydrofuran.
Disclosure of Invention
The technical problems to be solved by the invention are that the existing preparation method of 3-halogenated tetrahydrofuran in the field is high in cost, complex in process and not suitable for industrial production, and further provides a preparation method of 3-halogenated tetrahydrofuran. The preparation method has the advantages of simple process, high yield, low cost, suitability for industrial production and higher industrial application value.
The invention solves the technical problem through the following technical scheme.
The invention provides a preparation method of 3-halogenated tetrahydrofuran, which comprises the following steps: reacting a compound shown in a formula I with a reducing agent in an organic solvent at the temperature of 0-85 ℃ to obtain the compound;
wherein R is 1 And R 2 Same, selected from chlorine or bromine;
the reducing agent is sodium borohydride or potassium borohydride;
the organic solvent is ethylene glycol dimethyl ether, 2-chloroethyl methyl ether, diethyl ether, tetrahydrofuran or methyl tetrahydrofuran.
In the preparation method, the molar ratio of the compound of the formula I to the reducing agent can be 1:0.25-1:1.2, preferably 1:0.3-1: 1.
In the preparation method, the reaction temperature is preferably 15-82 ℃, more preferably 40-50 ℃ or 78-82 ℃.
In the preparation method, the reaction time is preferably 1-24hr, more preferably 3-6 hr.
In the preparation method, the mass ratio of the organic solvent to the compound of the formula I is 1:1-10:1, preferably 3:1-5:1, and more preferably 4: 1.
In the preparation method, the feeding sequence of the reaction can be the feeding sequence conventional in the field, and preferably the organic solvent, the reducing agent and the compound of the formula I are sequentially added at 40-50 ℃ or 78-82 ℃ for reaction; wherein the manner of addition of the compound of formula I is preferably dropwise. Another preferable feeding mode is that the organic solvent, the compound of the formula I and the reducing agent are sequentially added at 40-50 ℃ for reaction.
In the preparation method, the reaction can be monitored by TLC or HPLC, and is generally used as the end point of the reaction when the compound shown in the formula I disappears.
In the preparation method, the method further comprises a post-treatment step, and the post-treatment step comprises the following operations: after the reaction is finished, quenching the reaction product by using water, filtering the reaction product, rectifying the filtrate to obtain a target product, and recycling the solvent.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the method takes sodium borohydride or potassium borohydride as a reducing agent to reduce 2, 3-dihalogenated tetrahydrofuran so as to prepare the 3-halogenated tetrahydrofuran. The method has the advantages of few reaction steps, simple process, high product yield up to 80-95%, low raw material cost, low equipment investment and high product price; in addition, the method has small pollution and is environment-friendly and suitable for large-scale industrial production.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
Example 1
564g of ethylene glycol dimethyl ether and 11.4g (0.3mol) of sodium borohydride are added into a 1L four-neck flask, the temperature is controlled to be 40-50 ℃, 141g (1mol) of 2, 3-dichlorotetrahydrofuran is dripped, and the temperature is kept for 5 hours at 40-50 ℃ after the dripping is finished. After the 2, 3-dichlorotetrahydrofuran is completely reacted, a small amount of water is added for quenching, then sodium salt is removed by filtration, and the filtrate is rectified to separate the solvent and the product, and the solvent can be recycled. 99.1g of 3-chlorotetrahydrofuran is obtained with a yield of about 93 percent and a finished product purity>99％。GC-MS R t ＝14.27min,m/z 106(ES+)。
Example 2
564g of ethylene glycol dimethyl ether and 11.4g (0.3mol) of sodium borohydride are added into a 1L four-necked bottle, 2, 3-dichlorotetrahydrofuran 141g (1mol) is added dropwise at the temperature of 78-82 ℃, and the temperature is kept for 5 hours at 78-82 ℃ after the dropwise addition. Working-up was carried out as in example 1 to give 93.8g of 3-chlorotetrahydrofuran in a yield of about 88% and a purity of the end product of > 99%.
Example 3
In a 1L four-necked flask, 564g of THF and 11.4g (0.3mol) of sodium borohydride are added, and 141g (1mol) of 2, 3-dichlorotetrahydrofuran is added dropwise under controlled temperature of 40-50 ℃, and after the addition is finished, the temperature is kept at 40-50 ℃ for 5 hours. Working-up was carried out as in example 1 to give 95.9g of 3-chlorotetrahydrofuran in a yield of about 90% and a purity of the end product of > 99%.
Example 4
564g of ethylene glycol dimethyl ether and 11.4g (0.3mol) of sodium borohydride are added into a 1L four-neck flask, 2, 3-dibromo tetrahydrofuran 229.9g (1mol) is dropwise added at the temperature of 40-50 ℃, and the temperature is kept for 5 hours at 40-50 ℃ after the dropwise addition. The workup was as in example 1 to give 138.9g of 3-bromotetrahydrofuran in a yield of about 92% and a purity of the finished product>99％。GC-MS R t ＝15.6min,m/z 150(ES+)。
Example 5
Adding 141g of ethylene glycol dimethyl ether and 11.4g (0.3mol) of sodium borohydride into a 1L four-neck flask, controlling the temperature to be 40-50 ℃, dropwise adding 141g (1mol) of 2, 3-dichlorotetrahydrofuran, and preserving the temperature for 5 hours at 40-50 ℃ after the dropwise adding is finished. Working-up was carried out as in example 1 to give 92.7g of 3-chlorotetrahydrofuran in a yield of about 87% and a purity of the end product of > 99%.
Example 6
1410g of ethylene glycol dimethyl ether and 11.4g (0.3mol) of sodium borohydride are added into a 2L four-neck flask, 141g (1mol) of 2, 3-dichlorotetrahydrofuran is added dropwise at the temperature of 40-50 ℃, and the temperature is kept for 5 hours at 40-50 ℃ after the dropwise addition. Working-up was carried out as in example 1 to give 99.1g of 3-chlorotetrahydrofuran in a yield of about 93% and a purity of the end product of > 99%.
Example 7
564g of ethylene glycol dimethyl ether and 9.5g (0.25mol) of sodium borohydride are added into a 1L four-neck flask, the temperature is controlled to be 40-50 ℃, 141g (1mol) of 2, 3-dichlorotetrahydrofuran is dripped, and the temperature is kept for 5 hours at 40-50 ℃ after the dripping is finished. The workup was as in example 1, giving 93.8g of 3-chlorotetrahydrofuran in about 88% yield and a final product purity of > 99%.
Example 8
564g of ethylene glycol dimethyl ether and 37.8g (1mol) of sodium borohydride are added into a 1L four-neck flask, the temperature is controlled to be 40-50 ℃, 141g (1mol) of 2, 3-dichlorotetrahydrofuran is dripped, and the temperature is kept for 5 hours at 40-50 ℃ after the dripping is finished. Working-up was carried out as in example 1 to give 95.9g of 3-chlorotetrahydrofuran in a yield of about 90% and a purity of the end product of > 99%.
Example 9
564g of ethylene glycol dimethyl ether and 16.2g (0.3mol) of potassium borohydride are added into a 1L four-neck flask, the temperature is controlled to be 40-50 ℃, 141g (1mol) of 2, 3-dichlorotetrahydrofuran is dripped, and the temperature is kept for 5 hours at 40-50 ℃ after the dripping is finished. The workup was as in example 1, giving 98g of 3-chlorotetrahydrofuran in a yield of about 92% and a final product purity of > 99%.
Example 10
564g of ethylene glycol dimethyl ether and 11.4g (0.3mol) of sodium borohydride are added into a 1L four-neck flask, the temperature is controlled to be 40-50 ℃, 141g (1mol) of 2, 3-dichlorotetrahydrofuran is dripped, and the temperature is kept for 3 hours at 40-50 ℃ after the dripping is finished. Working-up as in example 1 gave 90.6g of 3-chlorotetrahydrofuran in a yield of about 85% and a purity of the product of > 99%.
Example 11
564g of ethylene glycol dimethyl ether and 11.4g (0.3mol) of sodium borohydride are added into a 1L four-neck flask, the temperature is controlled to be 40-50 ℃, 141g (1mol) of 2, 3-dichlorotetrahydrofuran is dripped, and the temperature is kept for 24 hours at 40-50 ℃ after the dripping is finished. The workup was as in example 1 to give 97g of 3-chlorotetrahydrofuran in a yield of about 91% and a purity of the finished product of > 99%.
Example 12
564g of ethylene glycol dimethyl ether and 141g (1mol) of 2, 3-dichlorotetrahydrofuran are added into a 1L four-necked flask, 11.4g (0.3mol) of sodium borohydride is slowly added at the temperature of 40-50 ℃, and the temperature is kept for 5 hours at 40-50 ℃ after the addition. The workup was as in example 1, giving 98g of 3-chlorotetrahydrofuran in a yield of about 92% and a final product purity of > 99%.
Example 13
564g of ethylene glycol dimethyl ether and 11.4g (0.3mol) of sodium borohydride are added into a 1L four-necked bottle, 2, 3-dichlorotetrahydrofuran 141g (1mol) is dripped at the temperature of 15-20 ℃, and the temperature is kept for 5 hours at 15-20 ℃ after the dripping is finished. The work-up was carried out as in example 1 to give 87.4g of 3-chlorotetrahydrofuran in a yield of about 82% and a purity of the product of > 99%.
Example 14
564g of ethylene glycol dimethyl ether and 11.4g (0.3mol) of sodium borohydride are added into a 1L four-neck flask, 141g (1mol) of 2, 3-dichlorotetrahydrofuran is added dropwise under the reflux at the temperature of 85 ℃, and the reflux and heat preservation are carried out for 5 hours at the temperature of 85 ℃ after the dropwise addition is finished. Working-up was carried out as in example 1 to give 88.4g of 3-chlorotetrahydrofuran in a yield of about 83% and a purity of the end product of > 99%.
Example 15
564g of ethylene glycol dimethyl ether and 11.4g (0.3mol) of sodium borohydride are added into a 1L four-neck flask, 141g (1mol) of 2, 3-dichlorotetrahydrofuran is dripped at the temperature of 0-5 ℃, and the temperature is kept for 5 hours at 0-5 ℃ after the dripping is finished. The work-up was carried out as in example 1 to give 85.2g of 3-chlorotetrahydrofuran in about 80% yield and a final product purity of > 99%.
Example 16
564g of diethyl ether and 11.4g (0.3mol) of sodium borohydride are added into a 1L four-neck flask, 2, 3-dichlorotetrahydrofuran 141g (1mol) is added dropwise at the temperature of 25-30 ℃, and the temperature is kept for 5 hours at 25-30 ℃ after the dropwise addition. Working-up was carried out as in example 1 to give 89.5g of 3-chlorotetrahydrofuran in a yield of about 84% and a purity of the end product of > 99%.
Comparative example 1
564g of isopropyl ether and 11.4g (0.3mol) of sodium borohydride are added into a 1L four-neck flask, the temperature is controlled to be 40-50 ℃, 141g (1mol) of 2, 3-dichlorotetrahydrofuran is added dropwise, and the temperature is kept for 5 hours at 40-50 ℃ after the dropwise addition is finished. The workup was as in example 1, giving 32g of 3-chlorotetrahydrofuran in about 30% yield and 98% purity of the finished product.
Comparative example 2
564g of ethylene glycol dimethyl ether and 11.4g (0.3mol) of sodium borohydride are added into a 1L four-mouth bottle, the temperature is controlled to be minus 10 to minus 5 ℃, 141g (1mol) of 2, 3-dichlorotetrahydrofuran is dripped, and the temperature is kept for 5 hours at minus 10 to minus 5 ℃ after the dripping is finished. Working-up was carried out as in example 1 to give 74.5g of 3-chlorotetrahydrofuran in a yield of about 70% and a purity of the product of > 99%.
Claims (11)
1. A process for the preparation of 3-halogenated tetrahydrofuran, comprising the steps of: reacting a compound shown in a formula I with a reducing agent in an organic solvent at the temperature of 0-85 ℃, and thus obtaining the compound;
wherein R is 1 And R 2 The same, are all selected from chlorine or bromine;
the reducing agent is sodium borohydride or potassium borohydride;
the organic solvent is ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, tetrahydrofuran or methyl furan.
2. The method of claim 1, wherein the molar ratio of the compound of formula I to the reducing agent is from 1:0.25 to 1: 1.2.
3. The method of claim 2, wherein the molar ratio of the compound of formula I to the reducing agent is from 1:0.3 to 1:1.
4. The method of claim 1, wherein the reaction temperature is from 15 ℃ to 82 ℃.
5. The method of claim 1, wherein the reaction temperature is 40-50 ℃ or 78-82 ℃.
6. The method of claim 1, wherein the reaction time is 1-24 hr.
7. The method of claim 6, wherein the reaction time is 3-6 hr.
8. The method of claim 1, wherein the mass ratio of the organic solvent to the compound of formula I is from 1:1 to 10: 1.
9. The method of claim 8, wherein the mass ratio of the organic solvent to the compound of formula I is from 3:1 to 5: 1.
10. The method of claim 9, wherein the mass ratio of the organic solvent to the compound of formula I is 4: 1.
11. The method of claim 1, further comprising a post-treatment step, the post-treatment step comprising the operations of: after the reaction is finished, quenching the reaction product by water, filtering the reaction product, and rectifying the filtrate to obtain a target product.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276559A (en) * | 2011-08-12 | 2011-12-14 | 河北威远生物化工股份有限公司 | Method for synthesizing 3-hydroxymethyl tetrahydrofuran |
| CN106749116A (en) * | 2016-11-29 | 2017-05-31 | 北京怡力生物科技有限公司 | A kind of preparation method of 3 amino methyl tetrahydrofuran |
| CN107098872A (en) * | 2017-03-23 | 2017-08-29 | 苏州华道生物药业股份有限公司 | A kind of production technology of the hydroxyl tetrahydrofuran of high-optical-purity 3 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276559A (en) * | 2011-08-12 | 2011-12-14 | 河北威远生物化工股份有限公司 | Method for synthesizing 3-hydroxymethyl tetrahydrofuran |
| CN106749116A (en) * | 2016-11-29 | 2017-05-31 | 北京怡力生物科技有限公司 | A kind of preparation method of 3 amino methyl tetrahydrofuran |
| CN107098872A (en) * | 2017-03-23 | 2017-08-29 | 苏州华道生物药业股份有限公司 | A kind of production technology of the hydroxyl tetrahydrofuran of high-optical-purity 3 |
Non-Patent Citations (2)
| Title |
|---|
| Reactions of chlorinated tetrahydrofurans. XIX.* Polychlorination of chlorotetrahydrofurans;K. ŠLAIS 等;《Chem. zvesti》;19771231;第31卷(第1期);109-117 * |
| β-Halogeno-ether Synthesis of Olefinic Alcohols: Stereochemistry of the Ring scission of 2-Substituted 3-Halogenotetrahydro-pyrans and -furans;Leslie Crombie 等;《J. CHEM. SOC. PERKIN TRANS.》;19851231;1983-1995 * |
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