CN102675080A - Preparation method of low-carbon chain symmetric anhydride - Google Patents
Preparation method of low-carbon chain symmetric anhydride Download PDFInfo
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- CN102675080A CN102675080A CN2012101699349A CN201210169934A CN102675080A CN 102675080 A CN102675080 A CN 102675080A CN 2012101699349 A CN2012101699349 A CN 2012101699349A CN 201210169934 A CN201210169934 A CN 201210169934A CN 102675080 A CN102675080 A CN 102675080A
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- AHDAMXUVQFHEDC-UHFFFAOYSA-N CC(C)C(C(OC(C(C(C)C)Br)=O)=O)Br Chemical compound CC(C)C(C(OC(C(C(C)C)Br)=O)=O)Br AHDAMXUVQFHEDC-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 application widely 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 needs the first acyl chlorides for preparing, again and carboxylic acid reaction; The preparation technology of this two-step approach is comparatively loaded down with trivial details, so this method usually is used for synthesizing asymmetric acid anhydrides.And the preparation of the symmetric anhydride of bibliographical information is a raw material with corresponding carboxylic acid mainly; Adopt (1) diacetyl oxide evaporation: this method is dewatering agent with the diacetyl oxide; With carboxylic acid reaction be the common reactant of synthetic acid anhydrides; But because diacetyl oxide participates in the 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 carboxylic acid reactions such as sulfur oxychloride, phosphorus trichloride, phosphorus pentachloride, POCl3, oxalyl chloride; Speed of response is very fast; But acyl chlorides by product and chloro acid anhydrides by product can occur, thereby influence productive rate and acid anhydrides purity, also having report to adopt phosgene/liquid phosgene/solid phosgene is dewatering agent; But toxicity is too big, also is not suitable for producing; (3) vitriol oil is a dewatering agent: because the vitriol oil itself contains less water, cause dewatering efficiency low, productive rate is low, after have report to improve to adopt oleum (being the sulphuric acid soln of sulphur trioxide), productive rate improves greatly, but toxicity is bigger, complex operation.(4) Vanadium Pentoxide in FLAKES is a dewatering agent: this method report is less, facts have proved on the laboratory scale and can carry out, but because Vanadium Pentoxide in FLAKES is a solid, cause the reaction system thickness, is difficult to stir and homogeneous reaction, therefore can't amplify scale.
Summary of the invention
Technical problem to be solved: have defectives such as preparing method's productive rate is low, complex operation now in order to solve the low carbon chain symmetric anhydride, 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 guarantee that post-processing operation is easy, the post-treating method that adopts comparatively simple distillation to purify.
Technical scheme: for solving the problems of the technologies described above, the present invention intends and adopts following technical scheme to prepare the low carbon chain symmetric anhydride:
With low carbon chain carboxylic acid (II) is raw material, through the reaction of the vitriol oil and Vanadium Pentoxide in FLAKES, distill low carbon chain symmetric anhydride (I), reaction formula is following:
Wherein, R is the naphthenic base of straight chained alkyl or the C3-6 of the straight chained alkyl of C1-5, substituted C1-4;
Said substituting group is halogen or methyl; Said halogen is fluorine, chlorine, bromine or iodine.
Wherein, described vitriol oil concentration is 98wt%.
Wherein, the mol ratio of the said vitriol oil and low carbon chain carboxylic acid (II) is (1 ~ 10): 1, and preferred 2: 1.
Wherein, said low carbon chain carboxylic acid (II) is (1 ~ 6) with the mol ratio of Vanadium Pentoxide in FLAKES: 1, and preferred 4: 1.
Wherein, said temperature of reaction is 30-150 ℃, preferred 80-100 ℃.
Wherein, the said reaction times is 1-10h, preferred 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, and is easy and simple to handle, is suitable for suitability for industrialized production, and gained low carbon chain symmetric anhydride purity is high.
Embodiment
To be illustrated representative embodiment of the present invention now, only be exemplary explanation, and the structure specified to physical data and these compounds of giving an example compound is consistent.But institute gives an actual example and does not limit the scope of the invention.
Embodiment 1: the preparation of diacetyl oxide.
Keep under 20 ℃ of the temperature, in 98% vitriol oil (98kg, 1000mol) in, add acetate (30kg while stirring successively; 500mol) and Vanadium Pentoxide in FLAKES (17.8kg 125mol), continue to stir 0.5h; Make its thorough mixing, react 3h down, 140 ℃ of cuts of air distillation collection in 80 ℃; Get 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).
Keep under 20 ℃ of the temperature, in 98% vitriol oil (196g, 2.0mol) in, add 2-gifblaar poison (78g while stirring successively; 1.0mol) and Vanadium Pentoxide in FLAKES (35.5g, 0.25mmol), continuation makes its thorough mixing after stirring 0.5h; Reaction 3h under 100 ℃, cut is collected in underpressure distillation, gets 2-gifblaar poison acid anhydride 59.2g; Productive rate 85.8%, the preparation of purity embodiment 3: two fluoro diacetyl oxide (2,2-difluoroacetic acid acid anhydride)
With reference to embodiment 2 methods, reaction times 5h collects 124-127 ℃ 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 ℃ of cut, productive rate 86.7%, purity (GC) 97.5%.
The preparation of embodiment 5:3-chloro pentane acid acid anhydride.
Keep under 20 ℃ of the temperature, in the vitriol oil (100g, 1.0mol) in, add 3-Mono Chloro Acetic Acid (13.7g while stirring successively; 0.1mol) and Vanadium Pentoxide in FLAKES (14.2g, 0.1mmol), after continuing to stir 0.5h; Make its thorough mixing, react 10h down, decompression collection cut in 80 ℃; Get 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
Keep under 20 ℃ of the temperature, in the vitriol oil (100g, 1.0mol) in, add 4-Mono Chloro Acetic Acid (13.7g while stirring successively; 0.1mol) and Vanadium Pentoxide in FLAKES (14.2g, 0.1mmol), after continuing to stir 0.5h; Make its thorough mixing, react 1h down, decompression collection cut in 100 ℃; Get 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)
Keep under 20 ℃ of the temperature, in the vitriol oil (60g, 0.6mol) in, add dichloro acetic acid (77.4g while stirring successively; 0.6mol) and Vanadium Pentoxide in FLAKES (14.2g, 0.1mmol), after continuing to stir 0.5h; Make its thorough mixing, react 1h down, decompression collection cut in 150 ℃; Get dichloro-diacetyl oxide 54.3g, productive rate 75.4%, purity (GC) 97.2%.
Embodiment 8: the preparation of Trichloroacetic anhydride (2,2, the 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 ℃ 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 ℃ 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 ℃ 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 of isobutyric anhydride (2 Methylpropionic acid acid anhydride).
With reference to the method for embodiment 2, normal pressure is collected 180-184 ℃ of cut, productive rate 77.5%, purity (GC) 97.5%.
Embodiment 17: the preparation of the preparation of trimethylacetic acid acid anhydride (2,2-dimethyl propylene acid anhydrides).
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 embodiment 21:2-chloro-3 Methylbutanoic acid acid anhydride.
With reference to the method for embodiment 2, cut, productive rate 87.1%, purity (GC) 97.6% are collected in decompression.
The preparation of embodiment 22:2-bromo-3 Methylbutanoic acid acid anhydride.
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 (10)
1. the preparation method of low carbon chain symmetric anhydride (I), it is characterized in that: with low carbon chain carboxylic acid (II) is raw material, through the vitriol oil and Vanadium Pentoxide in FLAKES reaction, distill low carbon chain symmetric anhydride (I), reaction formula is following:
Wherein, R is the naphthenic base of straight chained alkyl or the C3-6 of the straight chained alkyl of C1-5, substituted C1-4;
Said substituting group is halogen or methyl; Said halogen is fluorine, chlorine, bromine or iodine.
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 said vitriol oil and low carbon chain carboxylic acid (II) is (1 ~ 10): 1.
4. the preparation method of low carbon chain symmetric anhydride according to claim 3 (I) is characterized in that: the mol ratio of the said vitriol oil and low carbon chain carboxylic acid (II) is 2: 1.
5. the preparation method of low carbon chain symmetric anhydride according to claim 1 (I) is characterized in that: said low carbon chain carboxylic acid (II) is (1 ~ 6) with the mol ratio of Vanadium Pentoxide in FLAKES: 1.
6. the preparation method of low carbon chain symmetric anhydride according to claim 5 (I) is characterized in that: said low carbon chain carboxylic acid (II) is 4: 1 with the mol ratio of Vanadium Pentoxide in FLAKES.
7. the preparation method of low carbon chain symmetric anhydride according to claim 1 (I) is characterized in that: said temperature of reaction is 30-150 ℃.
8. the preparation method of low carbon chain symmetric anhydride according to claim 7 (I) is characterized in that: said temperature of reaction is 80-100 ℃.
9. the preparation method of low carbon chain symmetric anhydride according to claim 1 (I) is characterized in that: the said reaction times is 1-10h.
10. the preparation method of low carbon chain symmetric anhydride according to claim 9 (I) is characterized in that: the said reaction times is 2-5h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183601A (en) * | 2013-01-30 | 2013-07-03 | 巨化集团技术中心 | Method for simultaneously preparing difluoro acetic anhydride and difluoro acetic ester |
| CN104803839A (en) * | 2015-03-20 | 2015-07-29 | 浙江理工大学 | Method for preparing trifluoroacetic anhydride |
| CN105492417A (en) * | 2014-08-05 | 2016-04-13 | 索尔维公司 | Process for the preparation of halogenated carboxylic anhydrides |
| WO2021226433A1 (en) * | 2020-05-08 | 2021-11-11 | Hyconix, Inc. | Process for generating acid anhydrides |
| WO2022236127A1 (en) * | 2021-05-06 | 2022-11-10 | Hyconix, Inc. | Integrated process for generating acid anhydrides |
| CN115490587A (en) * | 2022-11-17 | 2022-12-20 | 苏州开元民生科技股份有限公司 | Synthesis method of trifluoroacetic anhydride |
-
2012
- 2012-05-28 CN CN201210169934.9A patent/CN102675080B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| RAM PARKASH,ET AL.: "Synthesis of tribromoacetic anhydride and its reaction with dimethyltin(Ⅳ)oxide", 《BULL.CHEM.SOC.JPN.》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183601A (en) * | 2013-01-30 | 2013-07-03 | 巨化集团技术中心 | Method for simultaneously preparing difluoro acetic anhydride and difluoro acetic ester |
| CN105492417A (en) * | 2014-08-05 | 2016-04-13 | 索尔维公司 | Process for the preparation of halogenated carboxylic anhydrides |
| CN104803839A (en) * | 2015-03-20 | 2015-07-29 | 浙江理工大学 | Method for preparing trifluoroacetic anhydride |
| WO2021226433A1 (en) * | 2020-05-08 | 2021-11-11 | Hyconix, Inc. | Process for generating acid anhydrides |
| CN115551800A (en) * | 2020-05-08 | 2022-12-30 | 纮康公司 | Process for producing acid anhydride |
| US11608306B2 (en) * | 2020-05-08 | 2023-03-21 | Hyconix, Inc. | Process for generating acid anhydrides |
| US20230120038A1 (en) * | 2020-05-08 | 2023-04-20 | Hyconix, Inc. | Process for generating acid anhydrides |
| WO2022236127A1 (en) * | 2021-05-06 | 2022-11-10 | Hyconix, Inc. | Integrated process for generating acid anhydrides |
| CN115490587A (en) * | 2022-11-17 | 2022-12-20 | 苏州开元民生科技股份有限公司 | Synthesis method of trifluoroacetic anhydride |
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