CN109384763A - The manufacturing method of 2- (2- halogenated ethyl) -1,3- dioxolanes - Google Patents
The manufacturing method of 2- (2- halogenated ethyl) -1,3- dioxolanes Download PDFInfo
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- CN109384763A CN109384763A CN201810875361.9A CN201810875361A CN109384763A CN 109384763 A CN109384763 A CN 109384763A CN 201810875361 A CN201810875361 A CN 201810875361A CN 109384763 A CN109384763 A CN 109384763A
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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
- C07D317/10—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 not condensed with other rings
- C07D317/14—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 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/16—Radicals substituted by halogen atoms or nitro radicals
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Abstract
The subject of the invention is to provide do not need appropriate managerial, the equipment for being suitable for the management etc., and the method for 2- (2- halogenated ethyl) -1,3-dioxolane is manufactured by the commercially available raw material that can be easy to get.It is the manufacturing method of the compound of formula (II) as solution, wherein react the compound of formula (I) with hydrogen halides in the presence of the solvent.[in formula, X is halogen atom]
Description
Technical field
The present invention relates to the useful 2- of the raw material of intermediate, polymer as medicine, pesticide etc. (2- halogenated ethyl) -1,
The manufacturing method of 3- dioxolanes.
Background technique
It is disclosed in patent document 1 and 2- (2- chloroethyl) -1,3- dioxolanes is manufactured by methacrylaldehyde, ethylene glycol and hydrogen chloride
Method, but in this method, in the processing of the methacrylaldehyde used as raw material, need appropriate managerial, be suitable for the management
Equipment etc..
It is disclosed in non-patent literature 1, by the 2- vinyl -1,3-dioxolane that can be easy to get, uses trimethyl
Silyl chloride (trimethylsilyl chloride) and sodium bromide, to manufacture 2- (2- bromoethyl) -1,3- dioxy penta
The method of ring, but yield is only 55%.In addition, this method needs the expensive trimethylsilyl chloride using excess quantity
Object, therefore be not only undesirable from the aspect of cost, but also generate due to not can avoid comprising trimethylsilyl chloride
The waste water of compound, its derivative, thus it is also not preferred from the viewpoint of Green Chemistry.
In the case where 2- (2- halogenated ethyl) -1,3-dioxolane is carried out industrial utilization, it is desired for high-purity, but
The stability of 2- (2- bromoethyl) -1,3-dioxolane is low, decompose in distillation purifying and yield reduce, therefore, it is difficult to
The target substance of high-purity is obtained in high yield.On the other hand, 2- (2- chloroethyl) -1,3-dioxolane is steady in distillation purifying
It is fixed, it is easily obtained the target substance of high-purity, in the industrial production, than 2- (2- bromoethyl) -1,3-dioxolane dominance.So
And also unknown 2- (2- chloroethyl) -1,3- bis- are manufactured by 2- vinyl -1,3-dioxolane that is cheap and being easy to get
The method of butyl oxide link.
Existing technical literature
Patent document
Patent document 1: U.S. Patent No. 2,432,601
Non-patent literature
Non-patent literature 1:Synthetic Communications, 15 (2), 87-89,1985
Summary of the invention
Problems to be solved by the invention
The object of the present invention is to provide: carrying capacity of environment is small, does not need appropriate managerial, the equipment for being suitable for the management etc.,
2- (2- halogenated ethyl) -1,3- dioxolanes, particularly 2- (2- chloroethene are manufactured by the commercially available raw material that can be easy to get
Base) -1,3- dioxolanes method.
The method used for solving the problem
The inventors of the present invention are studied in order to solve the above problems, as a result, it has been found that, by that commercially available product can be used as to obtain
2- vinyl -1,3- dioxolanes come highly selective, high yield and cost-effective manner and manufacture 2- (2- halogenated ethyl) -1,
The method of 3- dioxolanes, so as to complete the present invention.
That is, the present invention provide formula (II) compound (hereinafter also referred to as compound (II)) manufacturing method (hereinafter,
Method referred to as of the invention), make the compound (hereinafter also referred to as compound (I)) of formula (I) in the presence of the solvent and halogenation
Hydrogen is reacted.
[in formula, X is halogen atom]
The effect of invention
It according to the method for the present invention, being capable of highly selective, high yield and cost-effective manner manufacture conduct medicine, pesticide
Deng intermediate, polymer useful 2- (2- the halogenated ethyl) -1,3- dioxolanes (compound (II)) of raw material.
Specific embodiment
Method of the invention is the manufacturing method of compound (II), which is characterized in that as shown in following reaction equations, makes chemical combination
Object (I) is reacted with hydrogen halides in the presence of the solvent.According to the method for the present invention, β are selectively introduced halogen.
[in formula, X is as described above]
Commercially available product can be used in compound (I), but can also be manufactured by method as known in the art.
In the present specification, halogen atom indicates chlorine atom, bromine atom or iodine atom.As hydrogen halides, as long as according to institute
Desired compound (II) comes any one of selective chlorination hydrogen, hydrogen bromide or hydrogen iodide.Hydrogen halides can be directly with gas
Body form uses, and the solution form that can also be obtained with being dissolved in aftermentioned solvent uses.As hydrogen halide, preferably
Dry hydrogen halide.
It about the usage amount of hydrogen halides, is waited according to the difference of reaction condition etc. without can broadly provide, but relative to change
It closes 1 mole of object (I), usually 1~10 mole, preferably 1~2 mole, more preferably 1~1.2 mole.According to reaction condition,
Also the amount outside the range can be used.
Method of the invention is usually in the presence of a solvent.As solvent, as long as not generating bad shadow to reaction
Loud solvent.As the example of solvent, the aromatic hydrocarbon series solvents such as benzene,toluene,xylene can be enumerated；Methylene chloride, 1,
The halogenated hydrocarbon system solvent such as 2- dichloroethanes, chloroform, carbon tetrachloride, chlorobenzene；Ether, t-butyl methyl ether, tetrahydrofuran, 1,4- bis-Alkane, 1,3- bis-The ether series solvents such as alkane；And the one kind or two or more mixed solvent in them.It can also be to reaction
In the range of not generating adverse effect, the solvent other than above-mentioned solvent is used.
The usage amount of solvent cannot be broadly according to the difference of the usage amount, the type of solvent, reaction condition of raw material etc.
Regulation, but relative to compound (I), usually 1 times of capacity~10 times capacity.
The reactive mode of method of the invention can be any one of intermittent, continous way.As with intermittent progress
The order by merging of raw material in the case where reaction, is not particularly limited, and can enumerate for example, (1) is in the solution of hydrogen halide
Compound (I) or its solution are added, (2) add hydrogen halide or its solution etc. in compound (I) or its solution.In addition,
The addition of raw material can be carried out once or separately be carried out, and can also continuously be added.
Reaction temperature and reaction time in method of the invention is different and different according to reaction condition etc., cannot be broadly
Regulation, but reaction temperature is usually -78~100 DEG C or so, preferably 0~50 DEG C or so, more preferably 0~30 DEG C or so, instead
It is usually 10 minutes~48 hours or so, preferably 30 minutes~12 hours or so, more preferably 30 minutes~1 hour between seasonable
Left and right.
After the completion of reaction, as needed, for example, passing through the conventional methods progress such as neutralization, extraction, washing, dry, distillation
Post-processing, compound (II) can be isolated, purified.For example, being obtained by compound (I) with reacting for hydrogen halides
Reaction mixture in comprising in the case where unreacted hydrogen halides, by with alkali (for example, sodium carbonate, potassium carbonate, cesium carbonate etc.
The hydroxide such as the bicarbonates such as carbonate, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide) aqueous solution carry out in
With, alternatively, by the way that the non-active gas such as nitrogen, argon gas are imported into reaction mixture, so as to remove, then, for example,
It can be purified by distillation, to obtain desired compound (II).
As particularly preferred embodiment of the invention, method of the invention also includes following step: being terminated in reaction
Afterwards, as needed, unreacted hydrogen halides is removed from resulting reaction mixture, and/or from reaction mixture, by chemical combination
Object (II) is purified.More specifically, the present invention also includes following methods [A]~[C].
The manufacturing method of the compound of [A] formula (II), it includes following step:
(1) compound of formula (I) is reacted with hydrogen halides in the presence of the solvent；
(2) unreacted hydrogen halides is removed from the reaction mixture obtained in (1).
[in formula, X is halogen atom]
The manufacturing method of the compound of [B] formula (II), it includes following step:
(1) compound of formula (I) is reacted with hydrogen halides in the presence of the solvent；
(2) from the reaction mixture obtained in (1), the compound of formula (II) is purified.
[in formula, X is halogen atom]
The manufacturing method of the compound of [C] formula (II), it includes following step:
(1) compound of formula (I) is reacted with hydrogen halides in the presence of the solvent；
(2) unreacted hydrogen halides is removed from the reaction mixture obtained in (1)；
(3) from the reaction mixture obtained in (2), the compound of formula (II) is purified.
[in formula, X is halogen atom]
From the viewpoint of reducing carrying capacity of environment, the removing of further preferred unreacted hydrogen halides is by being not accompanied by
With the generation of caused waste water, importing non-active gas (nitrogen, argon gas etc.) Lai Jinhang into reaction mixture.In the situation
Under, if the importing of non-active gas by the way that well known to a person skilled in the art methods to carry out, for example, can be by will be non-
The pH value that active gases (nitrogen, argon gas etc.) is bubbled into reaction mixture until reaction mixture is come until becoming 3~5 or so
It carries out.
The purifying of compound (II) is preferably carried out by distilling.In this case, compound (II) by distill into
As long as capable purifying by the way that well known to a person skilled in the art methods to carry out, for example, can under reduced pressure (about 30~
80hpa), it is carried out under about 70~100 DEG C of tower top temperature.
Various constituent elements in method of the invention can suitably be selected from above-mentioned multiple illustrations, condition, also, can
To be combined with each other.That is, compound (I), hydrogen halides and solvent respective type, use form or usage amount；Reaction temperature；
Reaction time；Operation etc. can be appropriate from the illustration of above-mentioned usual range, the illustration of condition and preferred range, condition
Selection, and it is possible to be combined with each other.
It is exemplified below an example of the preferred embodiment of the present invention, but the present invention is not limited thereto.
[1] manufacturing method of the compound of formula (II), wherein
React the compound of formula (I) in the presence of the solvent, with hydrogen halides.
[in formula, X is halogen atom]
[2] method according to above-mentioned [1], X are chlorine atom.
[3] method according to above-mentioned [1] or [2], solvent be selected from aromatic hydrocarbon series solvent, halogenated hydrocarbon system solvent,
With it is one kind or two or more in ether series solvent.
[4] method according to any one of above-mentioned [1]~[3], also includes following step: resulting reaction is mixed
Object is closed to be neutralized with alkali.
[5] method according to above-mentioned [4], neutralization temperature are 0~10 DEG C.
[6] method according to any one of above-mentioned [1]~[3], also includes following step: mixed to resulting reaction
It closes in object and imports non-active gas.
[7] method according to above-mentioned [6], non-active gas are nitrogen.
[8] method according to any one of above-mentioned [1]~[7], also includes following step: by distillation, by formula
(II) compound is purified.
Embodiment
Next the embodiment of the present invention is recorded, but the present invention is not limited thereto and explains.
Embodiment 1
Methylene chloride 238g is added in 500ml four-hole boiling flask, it is cooling until 5 DEG C with ice water.Import hydrogen chloride gas
27.5% 2- vinyl -1,3-dioxolane dichloromethane solution 36.4g was then added dropwise in 19g through 30 minutes.In the temperature
Lower stirring 2 hours, it is then additional to import hydrogen chloride gas 4g, it futher stirs 1 hour.Reaction solution is water-soluble with 10% sodium carbonate
After liquid neutralizes, liquid separation is carried out, organic layer is dry with sodium sulphate, it is filtered, is concentrated under reduced pressure.By resulting concentrate by subtracting
Pressure distillation (65hPa, 110 DEG C of bath temperature) purified, with 6.0g (yield: 44%), purity 99.0% obtain 2- (2- chloroethene
Base) -1,3- dioxolanes.
The NMR spectra data of resulting 2- (2- chloroethyl) -1,3- dioxolanes are as described below.
1H-NMR(CD3Cl) δ 5.04 (t, J=5.0Hz, 1H), 4.00-3.95 (m, 2H), 3.90-3.85 (m, 2H),
3.65 (t, J=6.5Hz, 2H), 2.14 (dt, J=6.5,5.0Hz, 2H)
Embodiment 2
95.3% 2- vinyl -1,3-dioxolane 40g and toluene 40g are added in 100ml four-hole boiling flask, uses ice water
Cooling is until 5 DEG C.Through 30 minutes importing hydrogen chloride gas 16.7g at 10 DEG C~20 DEG C, then stir 30 minutes.20 DEG C with
Under, reaction solution is neutralized with 10% aqueous sodium carbonate of 1.5 times of capacity, organic layer saturated common salt water washing is used
Sodium sulphate is dry, is filtered.By resulting filtrate decompression distill (65hPa, 88 DEG C of tower top temperature), with 38.2g (yield:
71%), purity 96.6% obtains 2- (2- chloroethyl) -1,3- dioxolanes.
Embodiment 3
93.3% 2- vinyl -1,3-dioxolane 20g and toluene 20g are added in 100ml four-hole boiling flask, uses ice water
Cooling is until 5 DEG C.Through 30 minutes importing hydrogen chloride gas 8.15g at 10 DEG C~20 DEG C, then stir 1 hour (pH value 2~
3).To reaction solution bubbling nitrogen 1 hour (pH value 3~4).Resulting solution is evaporated under reduced pressure (65hPa, 88 DEG C of tower top temperature),
With 19.1g (yield: 73%), purity 96.8% obtain 2- (2- chloroethyl) -1,3- dioxolanes.
Embodiment 4
96.3% 2- vinyl -1,3-dioxolane 40g and toluene 20g are added in 100ml four-hole boiling flask, uses ice water
Cooling is until 5 DEG C.Through 45 minutes importing hydrogen chloride gas 16.8g at 12 DEG C~20 DEG C, 1 hour (pH value 2) is then stirred.It is right
Reaction solution is bubbled 1 hour nitrogen (pH value 4).Resulting solution is evaporated under reduced pressure (65hPa, 88 DEG C of tower top temperature), with 41.1g
(yield: 77%), purity 98.8% obtain 2- (2- chloroethyl) -1,3- dioxolanes.
Claims (8)
1. the manufacturing method of the compound of formula (II), wherein make the compound of formula (I) in the presence of the solvent and hydrogen halides into
Row reaction,
In formula, X is halogen atom.
2. according to the method described in claim 1, X is chlorine atom.
3. method according to claim 1 or 2, solvent is selected from aromatic hydrocarbon series solvent, halogenated hydrocarbon system solvent and ether system
It is one kind or two or more in solvent.
4. method described in any one of claim 1 to 3, also includes following step: by resulting reaction mixture
It is neutralized with alkali.
5. according to the method described in claim 4, neutralization temperature is 0~10 DEG C.
6. method described in any one of claim 1 to 3, also includes following step: to resulting reaction mixture
Middle importing non-active gas.
7. according to the method described in claim 6, non-active gas is nitrogen.
8. method according to any one of claims 1 to 7, also includes following step: by distillation, by formula (II)
Compound is purified.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017152289 | 2017-08-07 | ||
| JP2017-152289 | 2017-08-07 |
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| CN109384763A true CN109384763A (en) | 2019-02-26 |
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| CN201810875361.9A Pending CN109384763A (en) | 2017-08-07 | 2018-08-03 | The manufacturing method of 2- (2- halogenated ethyl) -1,3- dioxolanes |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2432601A (en) * | 1942-12-12 | 1947-12-16 | Du Pont | Polymers of alpha-methylene cyclic acetals |
| US5688973A (en) * | 1994-09-30 | 1997-11-18 | Degussa Aktiengesellschaft | Process for the production of 2-vinyl-1,3-dioxolane |
| JP2016084325A (en) * | 2014-10-28 | 2016-05-19 | 公立大学法人大阪府立大学 | Method for producing bromine-containing cyclic acetal compound |
-
2018
- 2018-08-02 JP JP2018145713A patent/JP7227711B2/en active Active
- 2018-08-03 CN CN201810875361.9A patent/CN109384763A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2432601A (en) * | 1942-12-12 | 1947-12-16 | Du Pont | Polymers of alpha-methylene cyclic acetals |
| US5688973A (en) * | 1994-09-30 | 1997-11-18 | Degussa Aktiengesellschaft | Process for the production of 2-vinyl-1,3-dioxolane |
| JP2016084325A (en) * | 2014-10-28 | 2016-05-19 | 公立大学法人大阪府立大学 | Method for producing bromine-containing cyclic acetal compound |
Non-Patent Citations (2)
| Title |
|---|
| HAROLD HIBBERT: ""STUDIES ON REACTIONS RELATING TO CARBOHYDRATES AND POLYSACCHARIDES. XXIII. SYNTHESIS AND PROPERTIES OF HYDROXY ALKYLIDENE GLYCOLS AND GLYCEROLS"", 《CARBOHYDRATES AND POLYSACCHARIDES. XXIII》 * |
| TSUTOMU KAGIYA等: ""Isomerization Polymerization of 2-Vinyl-1,3-dioxolane by α,α’-Azobisisobutyronitrile or by γ-Ray Irradiation"", 《JOURNAL OF POLYMER SCIENCE: PART A-1》 * |
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| JP2019031485A (en) | 2019-02-28 |
| JP7227711B2 (en) | 2023-02-22 |
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