CN108864035A - A kind of synthetic method of perhalogeno heterocycloalkane - Google Patents
A kind of synthetic method of perhalogeno heterocycloalkane Download PDFInfo
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- CN108864035A CN108864035A CN201810620813.9A CN201810620813A CN108864035A CN 108864035 A CN108864035 A CN 108864035A CN 201810620813 A CN201810620813 A CN 201810620813A CN 108864035 A CN108864035 A CN 108864035A
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- perhalogeno
- alkane
- heterocycloalkane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
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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
- C07D317/32—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/42—Halogen atoms or nitro radicals
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Abstract
The invention discloses a kind of synthetic method of perhalogeno heterocycloalkane, biacetyl oxygroup halogenated alkane oxo heterocycle alkane corresponding with the generation of perhalogeno diacid reactant, oxo heterocycle alkane is reacted with halide reagent again generates target product perhalogeno heterocycloalkane.The present invention is free of not complete fully halogenated hydrogeneous halogenated heterocyclic alkane, the corrosion-resistant and anti-aging property of polymer can be improved by the way that reaction of the invention, product perhalogeno heterocycloalkane can be realized in common glass reactor ware or pressure reaction still.Solve the problems, such as technology there are reaction temperature height, severe reaction conditions, there are endless fully halogenated hydrogeneous halogenated heterocyclic alkane.
Description
Technical field
The invention belongs to chemical technology fields, are specially related to a kind of synthetic method of perhalogeno heterocycloalkane.
Background technique
The perfluoro oxa- cycloalkane in perhalogeno heterocycloalkane, especially (the bromine, iodine) generation Han dichloro, can be anti-by dehalogenation
Perfluoro oxa- cycloolefin should be generated.Perfluoro oxa- cycloolefin is a kind of very important fluorochemical monomer, is used to prepare fluorine-containing
Unformed homopolymer can also prepare novel nothing with monomers copolymerization such as ethylene, propylene, tetrafluoroethene, trifluoro propene, chlorotrifluoroethylene
Sizing fluorinated copolymer.This kind of novel fluoroplastics have low refractive index and low dielectric constant, good translucency, Yi Jiyou
Different corrosion-resistant and ageing properties can be used as the insulation encapsulating material of optical cable foreskin coating and large scale integrated circuit element.
Perhalogeno heterocycloalkane synthetic method general at present is the heterocycloalkane halogen by heterocycloalkane or partially halogenated
Element carries out halogenation, obtains perhalogeno heterocycloalkane.For this method there are reaction temperature height, the hydrogen on alkane has been difficult to fully halogenated lack
Point.The presence of hydrogen atoms impurity can cause that chain tra nsfer occurs in polymerization process, cause polymer molecular weight to reduce, is poly-
The defects of closing the decline of object stability.
Document (US5177224) reports the Lewis acid catalyst chlorination 2,2- bis- (three of load on the activated carbon
Methyl fluoride) -1,3- dioxolane generates 2,2- bis- (trifluoromethyl) -1,3- dioxa tetrachloro pentamethylene, and reaction temperature is big
In 250 DEG C.Intermediate product containing a large amount of endless perhalogeno in product.
Document (US3749791) uses the method synthesizing halogen heterocycloalkane of Light chlorimation, and chlorine is passed through in a manner of being bubbled,
What is obtained is the halogenated heterocyclic alkane of partial oxidation.
Summary of the invention
Present invention aims at provide a kind of synthesis of perhalogeno heterocycloalkane for deficiency of the prior art
Method.For the present invention by the way that reaction of the invention can be realized in common glass reactor ware or pressure reaction still, product is complete
Halogenated heterocyclic alkane is free of not complete fully halogenated hydrogeneous halogenated heterocyclic alkane, and the corrosion-resistant and ageing resistance of polymer can be improved
Energy.Solving technology, there are reaction temperature height, severe reaction conditions, asking there are endless fully halogenated hydrogeneous halogenated heterocyclic alkane
Topic.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：
A kind of synthetic method of perhalogeno heterocycloalkane, it is characterised in that：Biacetyl oxygroup halogenated alkane and perhalogeno two
Acid reaction generates corresponding oxo heterocycle alkane, and oxo heterocycle alkane is reacted with halide reagent again generates target product perhalogeno heterocycle
Alkane.
Further, the biacetyl oxy substituents in biacetyl oxygroup halogenated alkane are connected on the same carbon atom, halogen
Element is the one or more of fluorine, chlorine, bromine, iodine.Biacetyl oxygroup halogenated alkane of the invention, can be biacetyl oxygroup perhalogeno
Alkane is also possible to the alkane of partially halogenated, but only biacetyl oxygroup all halogenated hydrocarbons, just available corresponding perhalogeno
Heterocycloalkane.
Further, the halogen in perhalogeno diacid is the one or more of fluorine, chlorine, bromine, iodine, the diacid in perhalogeno diacid
For the acid of the one or several carbon atoms of adjacent acid or interval.Adjacent acid, such as oxalic acid are spaced one or several carbon atoms
Acid, such as dihalo malonic acid, four halogenated succinimide acid.
Further, the molar ratio of biacetyl oxygroup halogenated alkane and perhalogeno diacid is 1：0.5~5.0, preferably 1：0.8
~2.0.The ratio of biacetyl oxygroup halogenated alkane and perhalogeno diacid does not have special limitation, for economics.Mole
Than outside the above range, reaction can also be normally carried out.Reaction can solvent or it is solvent-free under the conditions of carry out, solvent can be
The inert polarity or nonpolar solvent that do not react with reaction system such as alkane, halogenated alkane, aromatic hydrocarbons, halogenated aryl hydrocarbon, contain nitro
Aromatic hydrocarbons, ionic liquid etc..1~20% Bronsted acid or lewis acid of biacetyl oxygroup halogenated alkane mass ratio is added, it can
Reaction is accelerated to carry out.Bronsted acid or lewis acid can be sulfuric acid, p-methyl benzenesulfonic acid, hydrogen chloride, methane sulfonic acid, iron chloride, chlorine
Change zinc, aluminium chloride etc..
Further, the reaction temperature of biacetyl oxygroup halogenated alkane and perhalogeno diacid is 20~180 DEG C, preferably 50~
150℃。
Further, halide reagent is the reagent that can convert carbonyl to halogen element, and halide reagent refers to chlorination and fluorination
Reagent.Such as phosphorus pentachloride, thionyl chloride, sulfur tetrafluoride, DAST, N, N- dimethyl -1,1,2,2- tetrafluoro ethamine etc..
Further, the equivalent proportion of oxo heterocycle alkane and halide reagent is 1：0.5~5, preferably 1：1~3.Molar ratio is upper
It states except range, reaction can also be normally carried out.Reaction can solvent or it is solvent-free under the conditions of carry out.
Further, the temperature that oxo heterocycle alkane is reacted with halide reagent is 20~200 DEG C, preferably 80~150 DEG C.
The present invention is by adopting the above-described technical solution, have the advantages that：
Biacetyl oxy substituents in biacetyl oxygroup halogenated alkane are connected on the same carbon atom, halogen be fluorine,
The one or more of chlorine, bromine, iodine.Biacetyl oxygroup halogenated alkane of the invention, can be biacetyl oxygroup all halogenated hydrocarbons,
It can be the alkane of partially halogenated, but only biacetyl oxygroup all halogenated hydrocarbons, just available corresponding perhalogeno heterocycle alkane
Hydrocarbon.Halogen in perhalogeno diacid is the one or more of fluorine, chlorine, bromine, iodine, the diacid in perhalogeno diacid be adjacent acid or
It is spaced the acid of one or several carbon atoms.Adjacent acid, such as oxalic acid are spaced the acid of one or several carbon atoms, such as dihalo third
Diacid, four halogenated succinimide acid etc..The molar ratio of biacetyl oxygroup halogenated alkane and perhalogeno diacid is 1：0.5~5.0, preferably
1：0.8~2.0.The ratio of biacetyl oxygroup halogenated alkane and perhalogeno diacid does not have special limitation, for economics.
Outside the above range, reaction can also be normally carried out molar ratio.Reaction can solvent or it is solvent-free under the conditions of carry out, solvent can
To be the inert polarity that do not reacted with reaction system or nonpolar solvent, such as alkane, halogenated alkane, aromatic hydrocarbons, halogenated aryl hydrocarbon, contain
Aromatic hydrocarbons, ionic liquid of nitro etc..1~20% Bronsted acid or the Louis of biacetyl oxygroup halogenated alkane mass ratio is added
Acid can accelerate reaction to carry out.Bronsted acid or lewis acid can be sulfuric acid, p-methyl benzenesulfonic acid, hydrogen chloride, methane sulfonic acid, chlorination
Iron, zinc chloride, aluminium chloride etc..The reaction temperature of biacetyl oxygroup halogenated alkane and perhalogeno diacid is 20~180 DEG C, preferably
50~150 DEG C.Halide reagent is the reagent that can convert carbonyl to halogen element, and halide reagent refers to chlorination and fluorination reagent.
Such as phosphorus pentachloride, thionyl chloride, sulfur tetrafluoride, DAST, N, N- dimethyl -1,1,2,2- tetrafluoro ethamine etc..Oxo heterocycle alkane
Equivalent proportion with halide reagent is 1：0.5~5, preferably 1：1~3.Molar ratio outside the above range, reaction can also normally into
Row.Reaction can solvent or it is solvent-free under the conditions of carry out.The temperature that oxo heterocycle alkane is reacted with halide reagent is 20~200
DEG C, preferably 80~150 DEG C.
Reaction of the invention, product perhalogeno can be realized in the present invention in common glass reactor ware or pressure reaction still
Not complete fully halogenated hydrogeneous halogenated heterocyclic alkane is free of for heterocycloalkane.The corrosion-resistant and anti-aging property of polymer can be improved.
Specific embodiment
For a kind of synthetic method of perhalogeno heterocycloalkane of the present invention, biacetyl oxygroup halogenated alkane and perhalogeno diacid are anti-
Corresponding oxo heterocycle alkane should be generated, oxo heterocycle alkane is reacted with halide reagent again generates target product perhalogeno heterocycle alkane
Hydrocarbon.
Biacetyl oxy substituents in the present invention in biacetyl oxygroup halogenated alkane are connected on the same carbon atom, halogen
Element is the one or more of fluorine, chlorine, bromine, iodine.Biacetyl oxygroup halogenated alkane of the invention, can be biacetyl oxygroup perhalogeno
Alkane is also possible to the alkane of partially halogenated, but only biacetyl oxygroup all halogenated hydrocarbons, just available corresponding perhalogeno
Heterocycloalkane.Halogen in perhalogeno diacid is the one or more of fluorine, chlorine, bromine, iodine, and the diacid in perhalogeno diacid is adjacent
The one or several carbon atoms of acid or interval acid.Adjacent acid, such as oxalic acid are spaced the acid of one or several carbon atoms, and such as two
Halogenated malonic acid, four halogenated succinimide acid etc..The molar ratio of biacetyl oxygroup halogenated alkane and perhalogeno diacid is 1：0.5~5.0,
Preferably 1：0.8~2.0.The ratio of biacetyl oxygroup halogenated alkane and perhalogeno diacid does not have special limitation, for economy
Property consider.Outside the above range, reaction can also be normally carried out molar ratio.Reaction can solvent or it is solvent-free under the conditions of into
Row, solvent can be the inert polarity that do not react with reaction system or nonpolar solvent, such as alkane, halogenated alkane, aromatic hydrocarbons, halogen
For aromatic hydrocarbons, the aromatic hydrocarbons containing nitro, ionic liquid etc..1~20% Bronsted acid of biacetyl oxygroup halogenated alkane mass ratio is added
Or lewis acid, reaction can be accelerated to carry out.Bronsted acid or lewis acid can be sulfuric acid, p-methyl benzenesulfonic acid, hydrogen chloride, methyl sulphur
Acid, iron chloride, zinc chloride, aluminium chloride etc..The reaction temperature of biacetyl oxygroup halogenated alkane and perhalogeno diacid is 20~180
DEG C, preferably 50~150 DEG C.Halide reagent is the reagent that can convert carbonyl to halogen element, halide reagent refer to chlorination and
Fluorination reagent.Such as phosphorus pentachloride, thionyl chloride, sulfur tetrafluoride, DAST, N, N- dimethyl -1,1,2,2- tetrafluoro ethamine etc..Oxo
The equivalent proportion of heterocycloalkane and halide reagent is 1：0.5~5, preferably 1：1~3.Outside the above range, reaction can also for molar ratio
It is normally carried out.Reaction can solvent or it is solvent-free under the conditions of carry out.The temperature that oxo heterocycle alkane is reacted with halide reagent is
20~200 DEG C, preferably 80~150 DEG C.
Reaction of the invention, product perhalogeno can be realized in the present invention in common glass reactor ware or pressure reaction still
Not complete fully halogenated hydrogeneous halogenated heterocyclic alkane is free of for heterocycloalkane.The corrosion-resistant and anti-aging property of polymer can be improved.
Embodiment 1：
In the 1000ml four-hole boiling flask with mechanical stirring, reflux condensing tube, bromo- 2, the 2- bis- of 329g (1.0mol) 1- is added
Acetoxyl group pentafluoropropane, 280g (2.0mol) difluoro malonic acid, 10g p-methyl benzenesulfonic acid, stirring, are warming up to 120 DEG C, periodically take
Sample analysis, when detecting after reaction, cooling separates to obtain 272g2- trifluoromethyl -2- difluorobromomethyl -4,6- dioxo -
Fluoro- 1, the 3- dioxane of 5- bis-, yield 78%.
In 1000ml pressure reaction still, the 2- trifluoromethyl -2- difluoro bromine first of 175g (0.5mol) above-mentioned preparation is added
Fluoro- 1, the 3- dioxane of base -4,6- dioxo -5- two, 300g methylene chloride, 324g sulfur tetrafluoride, stirring are being warming up to
It is reacted at 120 DEG C, after reaction, refrigerated separation obtains 106g2- trifluoromethyl -2- difluorobromomethyl -4,4, and 6,6- tetra-
Corresponding hydrogeneous dioxane impurity is not detected in fluoro- 1, the 3- dioxane of fluoro- 5- bis-, yield 54%.
Embodiment 2：
In the 500ml four-hole boiling flask with mechanical stirring, reflux condensing tube, 268g (1.0mol) 2,2- diethyl acyl-oxygen is added
Base hexafluoropropane, 108g oxalic acid (1.2mol), the 5g concentrated sulfuric acid, stirring are warming up to 140 DEG C, and timing sampling analysis is anti-when detecting
It is cooling after answering, separate to obtain 201.5g2,2- bis- (trifluoromethyl) -4,5- dioxo -1,3- dioxolane, yield
84.7%.
In the 1000ml four-hole boiling flask with mechanical stirring, reflux condensing tube, addition 312g (1.5mol) phosphorus pentachloride,
2,2- bis- (trifluoromethyl) -4,5- dioxo -1,3- dioxane of 500g phosphorus oxychloride and 119g (0.5mol) above-mentioned preparation
Pentane, stirring, is heated to 100 DEG C, and reacted at 100 DEG C.After reaction, refrigerated separation obtains 142g2,2- bis- (three
Methyl fluoride) -4,4,5,5- tetra- chloro- 1,3- dioxolane, corresponding hydrogeneous dioxolane is not detected in yield 81.6%
Impurity.
Embodiment 3：
In the 1000ml four-hole boiling flask with mechanical stirring, reflux condensing tube, 301g (1.0mol) 1,3- bis- chloro- 2 is added,
2- diacetoxy tetrafluoropropane, 180g (2mol) oxalic acid, 30g ferric trichloride, 300g1- ethyl-3-methylimidazole tetrafluoro boric acid
Salt, stirring are warming up to 50 DEG C, and timing sampling analysis, when detecting after reaction, cooling separates to obtain 250.7g2,2- bis- (two
Fluorine chloromethyl) -4,5- dioxo -1,3- dioxolane, yield 92.5%.
In the 1000ml four-hole boiling flask with mechanical stirring, reflux condensing tube, 136g (0.5mol) above method system is added
Standby 2,2- bis- (difluorochloromethyl) -4,5- dioxo -1,3- dioxolane, 100gDMF, stirring is warming up to 70 DEG C, drop
Add 357g (3.0mol) thionyl chloride, after thionyl chloride is added dropwise to complete, is reacted under reflux conditions.After reaction, cold
But chloro- 1, the 3- dioxolane of 85.5g2,2- bis- (difluorochloromethyl) -4,4,5,5- tetra- is separated to obtain, yield 45% is not detected
Corresponding hydrogeneous dioxolane impurity.
Embodiment 4：
In the 500ml four-hole boiling flask with mechanical stirring, reflux condensing tube, 390g (1.0mol) 1,3- bis- bromo- 2 is added,
2- diacetoxy tetrafluoropropane, 90g (1mol) oxalic acid, the 10g concentrated sulfuric acid, stirring are warming up to 150 DEG C, and timing sampling is analyzed, really
It is fixed that cooling separates to obtain 290.5g2,2- bis- (difluorobromomethyl) -4,5- dioxo -1,3- dioxolane after reaction,
Yield 80.7%.
In the 1000ml four-hole boiling flask with mechanical stirring, reflux condensing tube, 180g (0.5mol) above method system is added
Standby 2,2- bis- (difluorobromomethyl) -4,5- dioxo -1,3- dioxolane, 208g (1mol) phosphorus pentachloride, 500g tri-
Chlorethoxyfos, stirring, are heated to 100 DEG C, are reacted.After reaction, refrigerated separation obtains 197g2,2- bis- (difluorobromomethyl)-
Corresponding hydrogeneous dioxolane is not detected in 4,4,5,5- tetra- chloro- 1,3- dioxolane, yield 84%.
The above is only specific embodiments of the present invention, but technical characteristic of the invention is not limited thereto.It is any with this hair
Based on bright, to realize essentially identical technical effect, made ground simple change, equivalent replacement or modification etc. are all covered
Among protection scope of the present invention.
Claims (8)
1. a kind of synthetic method of perhalogeno heterocycloalkane, it is characterised in that：Biacetyl oxygroup halogenated alkane and perhalogeno diacid
Reaction generates corresponding oxo heterocycle alkane, and oxo heterocycle alkane is reacted with halide reagent again generates target product perhalogeno heterocycle alkane
Hydrocarbon.
2. a kind of synthetic method of perhalogeno heterocycloalkane according to claim 1, it is characterised in that：Biacetyl oxygroup halogen
It is connected on the same carbon atom for the biacetyl oxy substituents in alkane, halogen is the one or more of fluorine, chlorine, bromine, iodine.
3. a kind of synthetic method of perhalogeno heterocycloalkane according to claim 1, it is characterised in that：In perhalogeno diacid
Halogen be fluorine, chlorine, bromine, iodine one or more, the diacid in perhalogeno diacid is that adjacent acid or interval are one or several
The acid of carbon atom.
4. a kind of synthetic method of perhalogeno heterocycloalkane according to claim 1, it is characterised in that：Biacetyl oxygroup halogen
It is 1 for the molar ratio of alkane and perhalogeno diacid：0.5~5.0, preferably 1：0.8~2.0.
5. a kind of synthetic method of perhalogeno heterocycloalkane according to claim 1, it is characterised in that：Biacetyl oxygroup halogen
It is 20~180 DEG C, preferably 50~150 DEG C for the reaction temperature of alkane and perhalogeno diacid.
6. a kind of synthetic method of perhalogeno heterocycloalkane according to claim 1, it is characterised in that：Halide reagent is can
Convert carbonyl to the reagent of halogen element, halide reagent refers to chlorination and fluorination reagent.
7. a kind of synthetic method of perhalogeno heterocycloalkane according to claim 1, it is characterised in that：Oxo heterocycle alkane
Equivalent proportion with halide reagent is 1：0.5~5, preferably 1：1~3.
8. a kind of synthetic method of perhalogeno heterocycloalkane according to claim 1, it is characterised in that：Oxo heterocycle alkane
The temperature reacted with halide reagent is 20~200 DEG C, preferably 80~150 DEG C.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0206673B1 (en) * | 1985-06-26 | 1989-09-27 | The Dow Chemical Company | Process for the preparation of meldrum's acid |
| CN104080780A (en) * | 2011-11-30 | 2014-10-01 | 索尔维公司 | Fluorinated derivatives of Meldrum's acid, a method for the preparation of the same, and their use as a solvent additive |
-
2018
- 2018-06-15 CN CN201810620813.9A patent/CN108864035A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0206673B1 (en) * | 1985-06-26 | 1989-09-27 | The Dow Chemical Company | Process for the preparation of meldrum's acid |
| CN104080780A (en) * | 2011-11-30 | 2014-10-01 | 索尔维公司 | Fluorinated derivatives of Meldrum's acid, a method for the preparation of the same, and their use as a solvent additive |
Non-Patent Citations (1)
| Title |
|---|
| YU.V.ZEIFMAN: "gem-Diacyloxy derivatives of polyfluoro ketones", 《RUSSIAN CHEMICAL BULLETIN》 * |
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Application publication date: 20181123 |