CN102675080B - Preparation method of low-carbon chain symmetric anhydride - Google Patents
Preparation method of low-carbon chain symmetric anhydride Download PDFInfo
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- CN102675080B CN102675080B CN201210169934.9A CN201210169934A CN102675080B CN 102675080 B CN102675080 B CN 102675080B CN 201210169934 A CN201210169934 A CN 201210169934A CN 102675080 B CN102675080 B CN 102675080B
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- QYSOWESBOUEDGH-UHFFFAOYSA-N C[BrH]C(C(OC(C([BrH]C)([BrH]C)[BrH]C)=O)=O)(Br)[BrH]C Chemical compound C[BrH]C(C(OC(C([BrH]C)([BrH]C)[BrH]C)=O)=O)(Br)[BrH]C QYSOWESBOUEDGH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of low-carbon chain symmetric anhydride (I). The preparation method comprises the following steps of: taking low-carbon chain carboxylic acid (II) as a raw material, performing reaction by concentrated sulfuric acid and phosphorus pentoxide, and distilling to obtain the high-purity low-carbon chain symmetric anhydride (I). The preparation method of the low-carbon chain symmetric anhydride, disclosed by the invention, only comprises one-step reaction, has the advantages of few reaction byproducts, high yield and simplicity and convenience in operation, and is suitable for industrial production; and the obtained low-carbon chain symmetric anhydride is high in purity.
Description
Technical field
The present invention relates to the field of chemical synthesis, be specifically related to the preparation method of low carbon chain symmetric anhydride.
Background technology
Acid anhydrides has a wide range of applications at chemical industry and field of medicaments, the method of the synthetic acid anhydrides of having reported at present has a lot, adopt acyl chlorides and carboxylic acid reaction can prepare acid anhydrides, but generally all need first to prepare acyl chlorides, again and carboxylic acid reaction, the preparation technology of this two-step approach is comparatively loaded down with trivial details, and therefore this method is usually used for synthesizing asymmetric acid anhydrides.And the preparation of the symmetric anhydride of bibliographical information is mainly taking corresponding carboxylic acid as raw material, adopt (1) diacetyl oxide evaporation: the method is taking diacetyl oxide as dewatering agent, with carboxylic acid reaction be the common reactant of synthetic acid anhydrides, but because diacetyl oxide participates in acid anhydrides forming process, this method very easily forms asymmetric acid anhydrides by product, thereby causes the drawback that aftertreatment is loaded down with trivial details and productive rate is not high; (2) chloro dehydrated reagent and the carboxylic acid reaction such as sulfur oxychloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, oxalyl chloride, speed of response is very fast, but there will be acyl chlorides by product and chloro acid anhydrides by product, thereby affect productive rate and acid anhydrides purity, also having report to adopt phosgene/liquid phosgene/solid phosgene is dewatering agent, but toxicity is too large, be also not suitable for producing; (3) vitriol oil is dewatering agent: because the vitriol oil itself contains a small amount of water, cause dewatering efficiency low, productive rate is low, after have Improvement of reports to adopt oleum (being the sulphuric acid soln of sulphur trioxide), productive rate improves greatly, but toxicity is larger, complex operation.(4) Vanadium Pentoxide in FLAKES is dewatering agent: the method report is less, facts have proved in laboratory scale and can carry out, but because Vanadium Pentoxide in FLAKES is solid, cause reaction system thickness, is difficult to stir and homogeneous reaction, therefore cannot amplify scale.
Summary of the invention
Technical problem to be solved: the defects such as the existing preparation method's productive rate of low carbon chain symmetric anhydride is low in order to solve, complex operation, the invention provides the method for the high purity low carbon chain symmetric anhydride that a kind of side reaction is few, productive rate is high, easy and simple to handle.In order to ensure that post-processing operation is easy, adopt the post-treating method of comparatively simple distilation.
Technical scheme: for solving the problems of the technologies described above, the present invention intends preparing by the following technical solutions low carbon chain symmetric anhydride:
Taking low carbon chain carboxylic acid (II) as raw material, through the vitriol oil and Vanadium Pentoxide in FLAKES reaction, distill to obtain low carbon chain symmetric anhydride (I), reaction formula is as follows:
Wherein, the straight chained alkyl that R is C1-5, the straight chained alkyl of C1-4 of replacement or the cycloalkyl of C3-6;
Described substituting group is halogen or methyl; Described halogen is fluorine, chlorine, bromine or iodine.
Wherein, described vitriol oil concentration is 98wt%.
Wherein, the mol ratio of the described vitriol oil and low carbon chain carboxylic acid (II) is (1 ~ 10): 1, and preferably 2: 1.
Wherein, described low carbon chain carboxylic acid (II) is (1 ~ 6) with the mol ratio of Vanadium Pentoxide in FLAKES: 1, and preferably 4: 1.
Wherein, described temperature of reaction is 30-150 DEG C, preferably 80-100 DEG C.
Wherein, the described reaction times is 1-10h, preferably 2-5h.
Beneficial effect:
The preparation method of low carbon chain symmetric anhydride of the present invention only comprises single step reaction, and this byproduct of reaction is few, and productive rate is high, easy and simple to handle, is suitable for suitability for industrialized production, and gained low carbon chain symmetric anhydride purity is high.
Embodiment
Now representative embodiment of the present invention being illustrated, is only exemplary explanation, and the structure specified with these compounds to the physical data of given an example compound is consistent.But example does not limit the scope of the invention.
Embodiment 1: the preparation of diacetyl oxide.
At 20 DEG C of maintenance temperature, in 98% vitriol oil (98kg, 1000mol), add successively while stirring acetic acid (30kg, 500mol) and Vanadium Pentoxide in FLAKES (17.8kg, 125mol), continue to stir 0.5h, it is fully mixed, at 80 DEG C, react 3h, 140 DEG C of cuts are collected in air distillation, obtain diacetyl oxide 22.8kg, productive rate 89.4%, purity (GC) 98.6%.
Embodiment 2: the preparation of fluoro diacetyl oxide (2-gifblaar poison acid anhydride).
At 20 DEG C of maintenance temperature, in 98% vitriol oil (196g, 2.0mol), add successively while stirring 2-gifblaar poison (78g, 1.0mol) and Vanadium Pentoxide in FLAKES (35.5g, 0.25mmol), continue to stir after 0.5h, it is fully mixed, at 100 DEG C, react 3h, cut is collected in underpressure distillation, obtain 2-gifblaar poison acid anhydride 59.2g, productive rate 85.8%, the preparation of purity example 3: two fluoro diacetyl oxide (2,2-difluoroacetic acid acid anhydride)
With reference to embodiment 2 methods, reaction times 5h, collects 124-127 DEG C of cut, productive rate 90.5%, purity (GC) 97.9%.
Embodiment 4: the preparation of chloracetic acid acid anhydride (2-sym-dichloroacetic anhydride)
With reference to embodiment 2 methods, collect 201-205 DEG C of cut, productive rate 86.7%, purity (GC) 97.5%.
The preparation of embodiment 5:3-chloro pentane acid acid anhydride.
At 20 DEG C of maintenance temperature, in the vitriol oil (100g, 1.0mol), add successively while stirring 3-Mono Chloro Acetic Acid (13.7g, 0.1mol) and Vanadium Pentoxide in FLAKES (14.2g, 0.1mmol), continue to stir after 0.5h, it is fully mixed, at 80 DEG C, react 10h, cut is collected in decompression, obtains 3-chloro pentane acid acid anhydride 5.4g, productive rate 42.3%, purity (GC) 98.1%.
The preparation of embodiment 6:4-chloro pentane acid acid anhydride
At 20 DEG C of maintenance temperature, in the vitriol oil (100g, 1.0mol), add successively while stirring 4-Mono Chloro Acetic Acid (13.7g, 0.1mol) and Vanadium Pentoxide in FLAKES (14.2g, 0.1mmol), continue to stir after 0.5h, it is fully mixed, at 100 DEG C, react 1h, cut is collected in decompression, obtains 4-chloro pentane acid acid anhydride 6.9g, productive rate 54.1%, purity (GC) 98.6%.
Embodiment 7: the preparation of dichloro acetic acid acid anhydride (2,2-dichloro acetic acid acid anhydride)
At 20 DEG C of maintenance temperature, in the vitriol oil (60g, 0.6mol), add successively while stirring dichloro acetic acid (77.4g, 0.6mol) and Vanadium Pentoxide in FLAKES (14.2g, 0.1mmol), continue to stir after 0.5h, it is fully mixed, at 150 DEG C, react 1h, cut is collected in decompression, obtains dichloro-diacetyl oxide 54.3g, productive rate 75.4%, purity (GC) 97.2%.
Embodiment 8: the preparation of Trichloroacetic anhydride (2,2,2-Trichloroacetic anhydride).
With reference to embodiment 2 methods, reaction times 5h, cut, productive rate 84.6%, purity (GC) 98.9% are collected in decompression.
Embodiment 9: the preparation of chlorodifluoroacetic acid acid anhydride (2-chloro-2,2-difluoroacetic acid acid anhydride).
With reference to embodiment 1 method, reaction times 2h, collects 93-96 DEG C of cut, productive rate 88.5%, purity (GC) 98.8%.
Embodiment 10: the preparation of monobromo-acetic acid acid anhydride (2-bromoacetic acid acid anhydride).
With reference to embodiment 2 methods, cut, productive rate 81.8%, purity (GC) 97.6% are collected in decompression.
Embodiment 11: the preparation of dibromoacetic acid acid anhydride (2,2-dibromoacetic acid acid anhydride).
With reference to embodiment 2 methods, cut, productive rate 65.2%, purity (GC) 97.3% are collected in decompression.
Embodiment 12: the preparation of tribromoacetic acid acid anhydride (2,2,2-tribromoacetic acid acid anhydride).
With reference to embodiment 2 methods, cut, productive rate 80.6%, purity (GC) 98.0% are collected in decompression.
Embodiment 13: the preparation of iodo diacetyl oxide (2-iodoacetic acid acid anhydride).
With reference to the feeding method of embodiment 2, reflux 3h, normal pressure is collected 48-50 DEG C of cut, productive rate 86.5%, purity (GC) 98.4%.
Embodiment 14: the preparation of propionic anhydride.
With reference to the method for embodiment 1, normal pressure is collected 170-172 DEG C of cut, productive rate 87.9%, purity (GC) 97.6%.
Embodiment 15: the preparation of butyryl oxide.
With reference to the method for embodiment 1, cut, productive rate 81.6%, purity (GC) 98.2% are collected in decompression.
Embodiment 16: the preparation of the preparation (2 Methylpropionic acid acid anhydride) of isobutyric anhydride.
With reference to the method for embodiment 2, normal pressure is collected 180-184 DEG C of cut, productive rate 77.5%, purity (GC) 97.5%.
Embodiment 17: the preparation of the preparation (PA acid anhydride) of trimethylacetic acid acid anhydride.
With reference to the method for embodiment 2, cut, productive rate 90.5%, purity (GC) 99.0% are collected in decompression.
The preparation of embodiment 18:2-neoprene acid anhydrides.
With reference to the method for embodiment 2, cut, productive rate 76.4%, purity (GC) 97.8% are collected in decompression.
The preparation of embodiment 19:2-bromo-butyric acid acid anhydride.
With reference to the method for embodiment 2, cut, productive rate 80.6%, purity (GC) 97.2% are collected in decompression.
The preparation of embodiment 20:2-iodine butyryl oxide.
With reference to the method for embodiment 2, cut, productive rate 72.5%, purity (GC) 98.5% are collected in decompression.
The preparation of the chloro-3 Methylbutanoic acid acid anhydride of embodiment 21:2-.
With reference to the method for embodiment 2, cut, productive rate 87.1%, purity (GC) 97.6% are collected in decompression.
The preparation of the bromo-3 Methylbutanoic acid acid anhydride of embodiment 22:2-.
With reference to the method for embodiment 2, cut, productive rate 80.2%, purity (GC) 98.0% are collected in decompression.
Embodiment 23:2, the preparation of 2-dimethyl butyrate acid anhydrides.
With reference to the method for embodiment 2, cut, productive rate 67.5%, purity (GC) 97.1% are collected in decompression.
Embodiment 24:3, the preparation of 3-dimethyl butyrate acid anhydrides.
With reference to the method for embodiment 2, cut, productive rate 81.2%, purity (GC) 98.4% are collected in decompression.
Embodiment 25: the preparation of valeric anhydride.
With reference to the method for embodiment 2, cut, productive rate 72.9%, purity (GC) 97.8% are collected in decompression.
Embodiment 26:2, the preparation of 2-dimethyl-penten acid anhydrides.
With reference to the method for embodiment 2, cut, productive rate 76.5%, purity (GC) 98.1% are collected in decompression.
Embodiment 27: the preparation of caproic anhydride.
With reference to the method for embodiment 2, cut, productive rate 80.7%, purity (GC) 97.4% are collected in decompression.
The preparation of embodiment 28:2-chloro pentane acid acid anhydride.
With reference to the method for embodiment 2, cut, productive rate 62.5%, purity (GC) 98.3% are collected in decompression.
Embodiment 29:2, the preparation of 2-dichloro valeric anhydride.
With reference to the method for embodiment 2, cut, productive rate 76.2%, purity (GC) 98.0% are collected in decompression.
The preparation of embodiment 30:2-bromine valeric anhydride.
With reference to the method for embodiment 2, cut, productive rate 79.6%, purity (GC) 97.7% are collected in decompression.
Embodiment 31: the preparation of cyclopropanecarboxylic acid acid anhydride.
With reference to the method for embodiment 2, cut, productive rate 54.9%, purity (GC) 99.2% are collected in decompression.
Embodiment 32: the preparation of cyclopentanecarboxylic acid acid anhydride.
With reference to the method for embodiment 2, cut, productive rate 66.8%, purity (GC) 97.5% are collected in decompression.
Embodiment 33: the preparation of heptanaphthenic acid acid anhydride.
With reference to the method for embodiment 2, cut, productive rate 61.9%, purity (GC) 98.2% are collected in decompression.
Claims (8)
1. the preparation method of low carbon chain symmetric anhydride (I), is characterized in that: taking low carbon chain carboxylic acid (II) as raw material, under the vitriol oil and Vanadium Pentoxide in FLAKES effect, react, distill to obtain low carbon chain symmetric anhydride (I), reaction formula is as follows:
Wherein, the straight chained alkyl that R is C1-5, the straight chained alkyl of C1-4 of replacement or the cycloalkyl of C3-6;
Described substituting group is halogen or methyl;
In the time that substituting group is methyl, the straight chained alkyl of the C1-4 of described replacement does not repeat with the straight chained alkyl of described C1-5;
Described halogen is fluorine, chlorine, bromine or iodine;
The mol ratio of the described vitriol oil and low carbon chain carboxylic acid (II) is 1～10:1;
Described low carbon chain carboxylic acid (II) is 1～6:1 with the mol ratio of Vanadium Pentoxide in FLAKES.
2. the preparation method of low carbon chain symmetric anhydride according to claim 1 (I), is characterized in that: described vitriol oil concentration is 98%.
3. the preparation method of low carbon chain symmetric anhydride according to claim 1 (I), is characterized in that: the mol ratio of the described vitriol oil and low carbon chain carboxylic acid (II) is 2:1.
4. the preparation method of low carbon chain symmetric anhydride according to claim 1 (I), is characterized in that: described low carbon chain carboxylic acid (II) is 4:1 with the mol ratio of Vanadium Pentoxide in FLAKES.
5. the preparation method of low carbon chain symmetric anhydride according to claim 1 (I), is characterized in that: described temperature of reaction is 30-150 DEG C.
6. the preparation method of low carbon chain symmetric anhydride according to claim 5 (I), is characterized in that: described temperature of reaction is 80-100 DEG C.
7. the preparation method of low carbon chain symmetric anhydride according to claim 1 (I), is characterized in that: the described reaction times is 1-10h.
8. the preparation method of low carbon chain symmetric anhydride according to claim 7 (I), is characterized in that: the described reaction times is 2-5h.
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| CN103183601B (en) * | 2013-01-30 | 2014-10-01 | 巨化集团技术中心 | Method for simultaneously preparing difluoro acetic anhydride and difluoro acetic ester |
| CN105492417B (en) * | 2014-08-05 | 2018-10-16 | 索尔维公司 | The method for being used to prepare the carboxylic acid anhydrides of halogenation |
| CN104803839B (en) * | 2015-03-20 | 2016-11-30 | 浙江理工大学 | A kind of method preparing trifluoroacetic anhydride |
| WO2021226433A1 (en) * | 2020-05-08 | 2021-11-11 | Hyconix, Inc. | Process for generating acid anhydrides |
| CN117677602A (en) * | 2021-05-06 | 2024-03-08 | 纮康公司 | Integrated process for producing anhydrides |
| CN115490587B (en) * | 2022-11-17 | 2023-03-03 | 苏州开元民生科技股份有限公司 | Synthesis method of trifluoroacetic anhydride |
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Non-Patent Citations (2)
| Title |
|---|
| Ram Parkash,et al..Synthesis of tribromoacetic anhydride and its reaction with dimethyltin(Ⅳ)oxide.《Bull.Chem.Soc.Jpn.》.1991,第64卷(第4期),第1443-1444页. |
| Synthesis of tribromoacetic anhydride and its reaction with dimethyltin(Ⅳ)oxide;Ram Parkash,et al.;《Bull.Chem.Soc.Jpn.》;199104;第64卷(第4期);第1443-1444页 * |
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