CN109748892A - A kind of preparation method of the halogenated tetrahydrofuran of 3- - Google Patents
A kind of preparation method of the halogenated tetrahydrofuran of 3- Download PDFInfo
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- CN109748892A CN109748892A CN201711093319.3A CN201711093319A CN109748892A CN 109748892 A CN109748892 A CN 109748892A CN 201711093319 A CN201711093319 A CN 201711093319A CN 109748892 A CN109748892 A CN 109748892A
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Abstract
The invention discloses a kind of preparation methods of the halogenated tetrahydrofuran of 3-.It the described method comprises the following steps: in organic solvent, at a temperature of 0-85 DEG C, Formulas I compound represented being reacted with reducing agent；Wherein, R1And R2It is identical, it is selected from chlorine or bromine；The reducing agent is sodium borohydride or potassium borohydride；The organic solvent is glycol dimethyl ether, 2- chloroethyl methyl ether, ether, tetrahydrofuran or methyltetrahydrofuran.Method reaction step of the present invention is few, simple process, and product yield is up to 80%-95%, and cost of material is low, and equipment investment is few, and product price is advantageous；Furthermore the method pollution is small, environmentally friendly, is suitble to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of preparation methods of the halogenated tetrahydrofuran of 3-.
Background technique
The halogenated tetrahydrofuran of 3- is the common intermediate of synthetic pesticide and medicine, and wherein 3- chlorine tetrahydrofuran is to prepare desinsection
The critical materials of agent dinotefuran, and the prior art preparation method is disclosed it is less, the reason is that 2 of tetrahydrofuran be easier
Replace, and 3 above replace then relative difficulty.
At present synthesis the halogenated tetrahydrofuran of 3- method mainly include the following types:
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.
For this article using tetrahydrofuran as raw material, first halogenating reaction obtains 2,3- dihalo tetrahydrofuran, then with tetrahydro aluminium
Lithium dechlorination obtains the halogenated tetrahydrofuran of 3-, yield 75%, but reducing agent Lithium Aluminium Hydride is more expensive, without 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
This article, for raw material, is equally restored to obtain 3- chlorine tetrahydrofuran, yield with Lithium Aluminium Hydride with 2,3- dichloro furans
81%, it is at high cost, be not suitable for industrialized production.
3. be raw material and elemental halogen as raw material using gamma-butyrolacton, first synthesize 3- it is halogenated-gamma-butyrolacton, then use reducing agent
Reduction obtain 2- it is halogenated -1,4-butanediol, then dehydrating agent effect under closed loop obtain the halogenated tetrahydrofuran of 3-.
Chinese patent application CN106749116A discloses following methods:
This method raw material is relatively cheap, but synthesis step is more, and easily open loop generates impurity during halogenating reaction, receives
Rate is lower, higher cost, is not suitable for industrialized production.
Therefore, this field needs to study a kind of new method for preparing the halogenated tetrahydrofuran of 3-.
Summary of the invention
The technical problem to be solved in the invention be the preparation method of the halogenated tetrahydrofuran of the current 3- in this field it is at high cost,
Complex process is not suitable for industrialized production, and then provides a kind of preparation method of halogenated tetrahydrofuran of 3-.The preparation method
Simple process, high income, at low cost, suitable industrialized production, industrial application value with higher.
The present invention is to solve technical problem by the following technical programs.
The present invention provides a kind of preparation methods of the halogenated tetrahydrofuran of 3-, the described method comprises the following steps: organic
In solvent, at a temperature of 0-85 DEG C, Formulas I compound represented is reacted with reducing agent；
Wherein, R1And R2It is identical, it is selected from chlorine or bromine；
The reducing agent is sodium borohydride or potassium borohydride；
The organic solvent is glycol dimethyl ether, 2- chloroethyl methyl ether, ether, tetrahydrofuran or methyl tetrahydro furan
It mutters.
In the preparation method, the molar ratio of the compound of formula I and reducing agent can be 1:0.25-1:1.2, preferably
For 1:0.3-1:1.
In the preparation method, the temperature of the reaction is preferably 15-82 DEG C, is more preferably 40-50 DEG C or 78-82
℃。
In the preparation method, the time of the reaction is preferably 1-24hr, is more preferably 3-6hr.
In the preparation method, the mass ratio of the organic solvent and compound of formula I is 1:1-10:1, preferably 3:
1-5:1 is more preferably 4:1.
In the preparation method, the charging sequence of the reaction can be the charging sequence of this field routine, preferably
Organic solvent, reducing agent and compound of formula I reaction are sequentially added at 40-50 DEG C or at 78-82 DEG C；It is wherein described
The mode that compound of formula I is added preferably is added dropwise.Another preferably feed way is organic molten to sequentially add at 40-50 DEG C
Agent, compound of formula I and reducing agent reaction.
In the preparation method, the reaction can be monitored by TLC or HPLC, generally with compound shown in Formulas I
As the terminal of reaction when disappearance.
In the preparation method, the method also includes post-processing step, the post-processing step includes following operation:
It is quenched with water, filters after reaction, filtrate rectifying obtains target product, and solvent is recyclable to be recycled.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can any combination to get the present invention it is each preferably
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
The present invention is using sodium borohydride or potassium borohydride as reducing agent reductase 12, and 3- dihalo tetrahydrofuran is to prepare 3-
Halogenated tetrahydrofuran.The reaction step of the method is few, simple process, and product yield is up to 80%-95%, and cost of material
Low, equipment investment is few, and product price is advantageous；Furthermore the method pollution is small, environmentally friendly, is suitble to large-scale industry metaplasia
It produces.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
Embodiment 1
Glycol dimethyl ether 564g, sodium borohydride 11.4g (0.3mol), temperature control 40- are added in the four-hole bottle of a 1L
Rear 40-50 DEG C of heat preservation 5hr is added dropwise in 50 DEG C of dropwise addition 2,3- dichloro tetrahydrofuran 141g (1mol).2,3- dichloro tetrahydrofuran
After fully reacting, a small amount of water quenching is added to go out, refilter removing sodium salt, filtrate rectifying separates solvent and product, recycled solvent.
Obtain 3- chlorine tetrahydrofuran 99.1g, yield about 93%, finished product purity > 99%.GC-MS Rt106 (ES of=14.27min, m/z
+)。
Embodiment 2
Glycol dimethyl ether 564g, sodium borohydride 11.4g (0.3mol), temperature control 78- are added in the four-hole bottle of a 1L
82 DEG C of dropwise addition 2,3- dichloro tetrahydrofuran 141g (1mol), 78-82 DEG C of heat preservation 5hr again after being added dropwise.Post-process same embodiment
1, obtain 3- chlorine tetrahydrofuran 93.8g, yield about 88%, finished product purity > 99%.
Embodiment 3
THF 564g, sodium borohydride 11.4g (0.3mol), 40-50 DEG C of temperature control dropwise addition are added in the four-hole bottle of a 1L
Enter 2,3- dichloro tetrahydrofuran 141g (1mol), 40-50 DEG C of heat preservation 5hr again after being added dropwise.Post-processing is obtained with embodiment 1
3- chlorine tetrahydrofuran 95.9g, yield about 90%, finished product purity > 99%.
Embodiment 4
Glycol dimethyl ether 564g, sodium borohydride 11.4g (0.3mol), temperature control 40- are added in the four-hole bottle of a 1L
50 DEG C of 2,3- of dropwise addition, bis- bromo tetrahydrofuran 229.9g (1mol), 40-50 DEG C of heat preservation 5hr again after being added dropwise.Post-processing is the same as real
Example 1 is applied, 3- bromine tetrahydrofuran 138.9g, yield about 92%, finished product purity > 99% are obtained.GC-MS Rt=15.6min, m/z
150(ES+)。
Embodiment 5
Glycol dimethyl ether 141g, sodium borohydride 11.4g (0.3mol), temperature control 40- are added in the four-hole bottle of a 1L
50 DEG C of dropwise addition 2,3- dichloro tetrahydrofuran 141g (1mol), 40-50 DEG C of heat preservation 5hr again after being added dropwise.Post-process same embodiment
1, obtain 3- chlorine tetrahydrofuran 92.7g, yield about 87%, finished product purity > 99%.
Embodiment 6
Glycol dimethyl ether 1410g, sodium borohydride 11.4g (0.3mol), temperature control 40- are added in the four-hole bottle of a 2L
50 DEG C of dropwise addition 2,3- dichloro tetrahydrofuran 141g (1mol), 40-50 DEG C of heat preservation 5hr again after being added dropwise.Post-process same embodiment
1, obtain 3- chlorine tetrahydrofuran 99.1g, yield about 93%, finished product purity > 99%.
Embodiment 7
Glycol dimethyl ether 564g, sodium borohydride 9.5g (0.25mol), temperature control 40- are added in the four-hole bottle of a 1L
Rear 40-50 DEG C of heat preservation 5hr is added dropwise in 50 DEG C of dropwise addition 2,3- dichloro tetrahydrofuran 141g (1mol).It post-processes with embodiment 1,
Obtain 3- chlorine tetrahydrofuran 93.8g, yield about 88%, finished product purity > 99%.
Embodiment 8
Glycol dimethyl ether 564g, sodium borohydride 37.8g (1mol), temperature control 40-50 are added in the four-hole bottle of a 1L
DEG C be added dropwise 2,3- dichloro tetrahydrofuran 141g (1mol), rear 40-50 DEG C of heat preservation 5hr is added dropwise.Post-processing is obtained with embodiment 1
To 3- chlorine tetrahydrofuran 95.9g, yield about 90%, finished product purity > 99%.
Embodiment 9
Glycol dimethyl ether 564g, potassium borohydride 16.2g (0.3mol), temperature control 40- are added in the four-hole bottle of a 1L
Rear 40-50 DEG C of heat preservation 5hr is added dropwise in 50 DEG C of dropwise addition 2,3- dichloro tetrahydrofuran 141g (1mol).It post-processes with embodiment 1,
Obtain 3- chlorine tetrahydrofuran 98g, yield about 92%, finished product purity > 99%.
Embodiment 10
Glycol dimethyl ether 564g, sodium borohydride 11.4g (0.3mol), temperature control 40- are added in the four-hole bottle of a 1L
Rear 40-50 DEG C of heat preservation 3hr is added dropwise in 50 DEG C of dropwise addition 2,3- dichloro tetrahydrofuran 141g (1mol).It post-processes with embodiment 1,
Obtain 3- chlorine tetrahydrofuran 90.6g, yield about 85%, finished product purity > 99%.
Embodiment 11
Glycol dimethyl ether 564g, sodium borohydride 11.4g (0.3mol), temperature control 40- are added in the four-hole bottle of a 1L
Rear 40-50 DEG C of heat preservation r for 24 hours is added dropwise in 50 DEG C of dropwise addition 2,3- dichloro tetrahydrofuran 141g (1mol).It post-processes with embodiment 1,
Obtain 3- chlorine tetrahydrofuran 97g, yield about 91%, finished product purity > 99%.
Embodiment 12
Glycol dimethyl ether 564g, 2,3- dichloro tetrahydrofuran 141g (1mol), control are added in the four-hole bottle of a 1L
Warm 40-50 DEG C is slowly added to sodium borohydride 11.4g (0.3mol), adds rear 40-50 DEG C of heat preservation 5hr.It post-processes with embodiment 1,
Obtain 3- chlorine tetrahydrofuran 98g, yield about 92%, finished product purity > 99%.
Embodiment 13
Glycol dimethyl ether 564g, sodium borohydride 11.4g (0.3mol), temperature control 15- are added in the four-hole bottle of a 1L
Rear 15-20 DEG C of heat preservation 5hr is added dropwise in 20 DEG C of dropwise addition 2,3- dichloro tetrahydrofuran 141g (1mol).It post-processes with embodiment 1,
Obtain 3- chlorine tetrahydrofuran 87.4g, yield about 82%, finished product purity > 99%.
Embodiment 14
Addition glycol dimethyl ether 564g, the sodium borohydride 11.4g (0.3mol) in the four-hole bottle of a 1L, 85 DEG C of temperature control
Reflux is lower to be added dropwise 2,3- dichloro tetrahydrofuran 141g (1mol), 85 DEG C of reflux heat preservation 5hr after being added dropwise.Post-process same embodiment
1, obtain 3- chlorine tetrahydrofuran 88.4g, yield about 83%, finished product purity > 99%.
Embodiment 15
Glycol dimethyl ether 564g, sodium borohydride 11.4g (0.3mol), temperature control 0-5 are added in the four-hole bottle of a 1L
DEG C be added dropwise 2,3- dichloro tetrahydrofuran 141g (1mol), rear 0-5 DEG C of heat preservation 5hr is added dropwise.Post-processing is obtained with embodiment 1
3- chlorine tetrahydrofuran 85.2g, yield about 80%, finished product purity > 99%.
Embodiment 16
Ether 564g, sodium borohydride 11.4g (0.3mol), 25-30 DEG C of temperature control dropwise addition are added in the four-hole bottle of a 1L
Rear 25-30 DEG C of heat preservation 5hr is added dropwise in 2,3- dichloro tetrahydrofuran 141g (1mol).Post-processing obtains 3- chlorine with embodiment 1
Tetrahydrofuran 89.5g, yield about 84%, finished product purity > 99%.
Comparative example 1
Isopropyl ether 564g, sodium borohydride 11.4g (0.3mol), 40-50 DEG C of temperature control drop are added in the four-hole bottle of a 1L
Add 2,3- dichloro tetrahydrofuran 141g (1mol), rear 40-50 DEG C of heat preservation 5hr is added dropwise.Post-processing obtains 3- with embodiment 1
Chlorine tetrahydrofuran 32g, yield about 30%, finished product purity 98%.
Comparative example 2
Glycol dimethyl ether 564g, sodium borohydride 11.4g (0.3mol), temperature control -10 are added in the four-hole bottle of a 1L
~-5 DEG C of dropwise addition 2,3- dichloro tetrahydrofuran 141g (1mol), -10~-5 DEG C of heat preservation 5hr after being added dropwise.Post-processing is the same as implementation
Example 1 obtains 3- chlorine tetrahydrofuran 74.5g, yield about 70%, finished product purity > 99%.
Claims (10)
1. a kind of preparation method of the halogenated tetrahydrofuran of 3-, which is characterized in that the described method comprises the following steps: in organic solvent
In, at a temperature of 0-85 DEG C, Formulas I compound represented is reacted with reducing agent；
Wherein, R1And R2It is identical, it is selected from chlorine or bromine；
The reducing agent is sodium borohydride or potassium borohydride；
The organic solvent is glycol dimethyl ether, 2- chloroethyl methyl ether, ether, tetrahydrofuran or methyltetrahydrofuran.
2. preparation method as described in claim 1, which is characterized in that the compound of formula I and the molar ratio of reducing agent are 1:
0.25-1:1.2。
3. preparation method as claimed in claim 2, which is characterized in that the compound of formula I and the molar ratio of reducing agent are 1:
0.3-1:1。
4. preparation method as described in claim 1, which is characterized in that the temperature of the reaction is 15-82 DEG C.
5. preparation method as described in claim 1, which is characterized in that the temperature of the reaction is 40-50 DEG C or 78-82 DEG C.
6. preparation method as described in claim 1, which is characterized in that the time of the reaction is 1-24hr, preferably 3-
6hr。
7. preparation method as described in claim 1, which is characterized in that the organic solvent and the mass ratio of compound of formula I are
1:1-10:1。
8. preparation method as claimed in claim 7, which is characterized in that the organic solvent and the mass ratio of compound of formula I are
3:1-5:1。
9. preparation method as claimed in claim 8, which is characterized in that the organic solvent and the mass ratio of compound of formula I are
4:1。
10. preparation method as described in claim 1, which is characterized in that the method also includes post-processing step, locate after described
Reason step includes following operation: being quenched with water, filters after reaction, filtrate rectifying obtains 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 |
-
2017
- 2017-11-08 CN CN201711093319.3A patent/CN109748892B/en active Active
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 |
|---|
| K. ŠLAIS 等: "Reactions of chlorinated tetrahydrofurans. XIX.* Polychlorination of chlorotetrahydrofurans", 《CHEM. ZVESTI》 * |
| LESLIE CROMBIE 等: "β-Halogeno-ether Synthesis of Olefinic Alcohols: Stereochemistry of the Ring scission of 2-Substituted 3-Halogenotetrahydro-pyrans and -furans", 《J. CHEM. SOC. PERKIN TRANS.》 * |
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