CN114349630A - Preparation method of deuterated trifluoroacetic acid - Google Patents
Preparation method of deuterated trifluoroacetic acid Download PDFInfo
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- CN114349630A CN114349630A CN202210179171.XA CN202210179171A CN114349630A CN 114349630 A CN114349630 A CN 114349630A CN 202210179171 A CN202210179171 A CN 202210179171A CN 114349630 A CN114349630 A CN 114349630A
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- trifluoroacetic acid
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- dehydrating agent
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- DTQVDTLACAAQTR-DYCDLGHISA-N trifluoroacetic acid-d1 Chemical compound [2H]OC(=O)C(F)(F)F DTQVDTLACAAQTR-DYCDLGHISA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 42
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 26
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010457 zeolite Substances 0.000 claims abstract description 26
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 24
- 229910052786 argon Inorganic materials 0.000 claims abstract description 19
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 16
- 230000005587 bubbling Effects 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 20
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 7
- 238000007792 addition Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 abstract description 3
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 12
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229940005657 pyrophosphoric acid Drugs 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910052805 deuterium Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RQHMQURGSQBBJY-UHFFFAOYSA-N (2,2-dichloroacetyl) 2,2-dichloroacetate Chemical compound ClC(Cl)C(=O)OC(=O)C(Cl)Cl RQHMQURGSQBBJY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PNQBEPDZQUOCNY-UHFFFAOYSA-N trifluoroacetyl chloride Chemical compound FC(F)(F)C(Cl)=O PNQBEPDZQUOCNY-UHFFFAOYSA-N 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 amino zeolite Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Abstract
The invention relates to a preparation method of deuterated trifluoroacetic acid, belonging to the technical field of fine chemical engineering and comprising the following steps: step one, soaking amino artificial zeolite in ammonium dihydrogen phosphate solution, performing suction filtration, washing, drying, roasting, grinding and sieving to obtain a dehydrating agent; step two, adding a solvent and a dehydrating agent into a dry reaction kettle, stirring and mixing, then dropwise adding trifluoroacetic acid under a stirring state, heating up for reflux reaction after complete dropwise adding, then distilling under normal pressure, collecting front fraction at 40-50 ℃, and rectifying the obtained front fraction to obtain trifluoroacetic anhydride; and step three, adding trifluoroacetic anhydride into a dry reaction kettle, introducing argon, forming argon bubbling, then dropwise adding heavy water at 0 +/-3 ℃, completely dropwise adding, bubbling for 1-1.5h with argon, and rectifying to obtain the deuterated trifluoroacetic acid. The invention adopts the dehydration function of the dehydrating agent, improves the purity of trifluoroacetic anhydride and improves the conversion rate of heavy water.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a preparation method of deuterated trifluoroacetic acid.
Background
Deuterated trifluoroacetic acid belongs to one of deuterated reagents, is commonly used as a detection reagent for nuclear magnetic detection of polymers, and has the following functions: increasing the solubility of the substance to be detected; exchange hydrogen and deuterium with hydrogen in a system to be detected, and eliminate the nuclear magnetic peak of active hydrogen; and (3) damaging hydrogen bonds in a system to be detected. The preparation of deuterated trifluoroacetic acid is firstly to prepare trifluoroacetic anhydride, and then the deuterated trifluoroacetic anhydride is hydrolyzed by trifluoroacetic anhydride and heavy water to obtain the deuterated trifluoroacetic acid. The method for obtaining trifluoroacetic anhydride comprises the following steps: reacting trifluoroacetyl chloride with sodium trifluoroacetate to obtain the product; 2, 2-dichloroacetic anhydride is taken as a dehydrating agent to dehydrate trifluoroacetic acid to obtain the compound; phosphorus pentoxide dehydrates trifluoroacetic acid. The trifluoroacetyl chloride has a low boiling point (boiling point: -27 ℃), and is industrially very inconvenient to prepare, store and use, 2, 2-dichloroacetic anhydride is expensive and unavailable, and the yield of the reaction is not high, so that the former two methods are used less. Phosphorus pentoxide and trifluoroacetic acid are commercialized, are cheap and are easily available, and the method becomes a main method for industrially preparing trifluoroacetic anhydride. However, in the method, phosphorus pentoxide is used as a raw material, so that the obtained trifluoroacetic anhydride contains a large amount of pyrophosphoric acid and phosphoric acid by-products, and the trifluoroacetic anhydride is difficult to remove by rectification. And both the pyrophosphoric acid and the phosphoric acid can exchange hydrogen and deuterium with deuterium in the heavy water, so that the conversion rate of the heavy water is reduced, and the production cost of an enterprise is increased.
Therefore, there is a need to improve the preparation of trifluoroacetic anhydride, reduce the contents of pyrophosphoric acid and phosphoric acid in trifluoroacetic anhydride, improve the conversion rate of heavy water, and reduce the production cost of enterprises.
Disclosure of Invention
The invention aims to provide a preparation method of deuterated trifluoroacetic acid, which aims to solve the technical problems mentioned in the background technology.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of deuterated trifluoroacetic acid comprises the following steps:
step one, adding a solvent and a dehydrating agent into a dry reaction kettle, stirring for 20-30min at 800r/min under 600-800r/min, then dropwise adding trifluoroacetic acid under the stirring state, wherein the dropping speed is 2-4 drops/second, after complete dropwise addition, heating and refluxing for 6-24h, then distilling under normal pressure, collecting front fraction at 40-50 ℃, and rectifying the obtained front fraction to obtain trifluoroacetic anhydride, wherein the feeding mass ratio of the dehydrating agent to the trifluoroacetic acid is 1: 2-5;
and step two, adding trifluoroacetic anhydride into a dry reaction kettle, introducing argon, forming the condition of argon bubbling, then dropwise adding heavy water at the temperature of 0 +/-3 ℃, wherein the dropping speed is 2-4 drops/second, after complete dropwise addition, argon bubbling is carried out for 1-1.5 hours at the temperature of 0-10 ℃, and then rectifying to obtain deuterated trifluoroacetic acid, wherein the molar ratio of the trifluoroacetic anhydride to the heavy water is 1: 1.05-1.2.
Further, the dehydrating agent is prepared by the following steps:
firstly, ultrasonically dispersing artificial zeolite in absolute ethyl alcohol, then adding 3-aminopropyl trimethoxy silane, heating and refluxing for 1.5-2h, then cooling to room temperature, performing ultrafiltration and drying to obtain the amino artificial zeolite, wherein the dosage ratio of the artificial zeolite, the absolute ethyl alcohol and the 3-aminopropyl trimethoxy silane is 1g:10-15mL:0.3-0.5g, and in the reaction, the amino is grafted on the surface of the artificial zeolite by utilizing the etherification reaction of hydroxyl on the surface of the artificial zeolite and methoxyl in the 3-aminopropyl trimethoxy silane under the reflux action;
secondly, soaking the amino artificial zeolite in ammonium dihydrogen phosphate solution for 1-1.5h by an equal volume soaking method, filtering, washing with deionized water, drying at the temperature of 100 ℃ and 120 ℃, heating to the temperature of 500 ℃ and 550 ℃ at the speed of 2 ℃/min, roasting for 4h, grinding through a sieve of 150 ℃ and 300 meshes to obtain a dehydrating agent, wherein the mass concentration of the ammonium dihydrogen phosphate solution is 25-45%, in the reaction, the adsorption effect of amino or hydroxyl on the surface of the amino artificial zeolite on dihydrogen phosphate ions is utilized, the dihydrogen phosphate ions are deposited on the surface of the amino zeolite in the soaking process, then the high-temperature roasting is utilized to generate phosphorus pentoxide on the surface of the modified zeolite, the adsorption effect of the amino on the dihydrogen phosphate ions is stronger than that of the hydroxyl, the deposition effect of the dihydrogen phosphate ions on the surface of the amino artificial zeolite is stronger than that on the surface of the artificial zeolite, therefore, the amino artificial zeolite can improve the load of the phosphorus pentoxide and improve the dehydration capability of the dehydrating agent.
The invention has the beneficial effects that:
the dehydrating agent is used for replacing the dehydrating effect of phosphorus pentoxide, the dehydrating agent is artificial zeolite loaded phosphorus pentoxide, the joint water absorption effect of the artificial zeolite and the phosphorus pentoxide is utilized, the dehydrating effect on trifluoroacetic acid is achieved, the phosphorus pentoxide is loaded in the artificial zeolite and does not exist in a free form, after the dehydrating agent absorbs water, the dehydrating agent expands to form a colloid substance, the excessive phosphorus pentoxide is avoided, the generation of pyrophosphoric acid (the generation condition of pyrophosphoric acid is the reaction of the excessive phosphorus pentoxide and water) is avoided, only few free phosphoric acid is generated, the subsequent purification of trifluoroacetic anhydride only needs simple rectification, the purity of the trifluoroacetic anhydride is improved, and the conversion rate of heavy water is improved; secondly, the dehydrating agent can be dehydrated at high temperature and then recycled after absorbing water;
thirdly, the invention adopts heavy water to drop trifluoroacetic anhydride, compared with the traditional method of dropping trifluoroacetic anhydride into water, the invention can reduce the use amount of heavy water, and shorten the reaction time by controlling the dropping speed and the temperature;
finally, the invention uses argon bubbling as the stirring function of a large amount of reaction liquid, maintains the inert gas environment and improves the controllability of the reaction.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of the dehydrating agent:
firstly, 100g of artificial zeolite is ultrasonically dispersed in 1000mL of absolute ethyl alcohol, then 30g of 3-aminopropyltrimethoxysilane is added, heating and refluxing are carried out for 1.5h, then the temperature is reduced to room temperature, ultrafiltration is carried out, and drying is carried out, thus obtaining the amino artificial zeolite;
and secondly, soaking the amino artificial zeolite in ammonium dihydrogen phosphate solution for 1 hour by adopting an isometric soaking method, performing suction filtration, washing with deionized water, drying at 100 ℃, heating to 500 ℃ at the speed of 2 ℃/min, roasting for 4 hours, grinding and sieving with a 150-mesh sieve to obtain the dehydrating agent, wherein the mass concentration of the ammonium dihydrogen phosphate solution is 25%.
Example 2
Preparation of the dehydrating agent:
firstly, dispersing 100g of artificial zeolite in 1500mL of absolute ethyl alcohol by ultrasonic waves, then adding 50g of 3-aminopropyltrimethoxysilane, heating and refluxing for 2 hours, then cooling to room temperature, ultrafiltering and drying to obtain the amino artificial zeolite;
secondly, soaking the amino artificial zeolite in ammonium dihydrogen phosphate solution for 1.5h by adopting an equal-volume soaking method, performing suction filtration, washing with deionized water, drying at 120 ℃, heating to 550 ℃ at the speed of 2 ℃/min, roasting for 4h, grinding and sieving with a 300-mesh sieve to obtain a dehydrating agent, wherein the mass concentration of the ammonium dihydrogen phosphate solution is 45 percent
Example 3
A preparation method of deuterated trifluoroacetic acid comprises the following steps:
step one, adding 400mL of toluene and 75g of the dehydrating agent prepared in the embodiment 1 into a dry reaction kettle, stirring for 20min at 600r/min, then dropwise adding 150g of trifluoroacetic acid under a stirring state at a dropping speed of 2 drops/second, heating for reflux reaction for 6h after complete dropwise addition, distilling at normal pressure, collecting front fraction at 40-50 ℃, and rectifying the obtained front fraction to obtain trifluoroacetic anhydride;
and step two, adding 0.1mol of trifluoroacetic anhydride into a dry reaction kettle, introducing argon, forming the condition of argon bubbling, then dropwise adding 0.105mol of heavy water at the temperature of 0 +/-3 ℃, wherein the dropwise adding speed is 2 drops/second, after completely dropwise adding, bubbling argon for 1 hour at the temperature of 0 ℃, and then rectifying to obtain the deuterated trifluoroacetic acid.
The conversion of heavy water was calculated to be 98.8%.
Example 4
A preparation method of deuterated trifluoroacetic acid comprises the following steps:
step one, adding 300mL of dimethylbenzene and 50g of dehydrating agent prepared in the embodiment 1 into a dry reaction kettle, stirring for 30min at 800r/min, then dropwise adding 150g of trifluoroacetic acid under a stirring state at a dropping speed of 4 drops/second, heating for reflux reaction for 12h after complete dropwise addition, then distilling at normal pressure, collecting front fraction at 40-50 ℃, and rectifying the obtained front fraction to obtain trifluoroacetic anhydride;
and step two, adding 0.1mol of trifluoroacetic anhydride into a dry reaction kettle, introducing argon, forming the condition of argon bubbling, then dropwise adding 0.105mol of heavy water at the temperature of 0 +/-3 ℃, wherein the dropwise adding speed is 3 drops/second, after completely dropwise adding, bubbling argon for 1.5 hours at the temperature of 5-6 ℃, and rectifying to obtain the deuterated trifluoroacetic acid.
The conversion of heavy water was calculated to be 99.1%.
Example 5
A preparation method of deuterated trifluoroacetic acid comprises the following steps:
step one, adding 300mL of chlorobenzene and 30g of the dehydrating agent prepared in the embodiment 1 into a dry reaction kettle, stirring for 30min at 600r/min, then dropwise adding 150g of trifluoroacetic acid under a stirring state at a dropping speed of 4 drops/second, heating for reflux reaction for 24h after complete dropwise addition, then distilling at normal pressure, collecting front fraction at 40-50 ℃, and rectifying the obtained front fraction to obtain trifluoroacetic anhydride;
and step two, adding 0.1mol of trifluoroacetic anhydride into a dry reaction kettle, introducing argon, forming the condition of argon bubbling, then dropwise adding 0.12mol of heavy water at the temperature of 0 +/-3 ℃, wherein the dropwise adding speed is 4 drops/second, after completely dropwise adding, bubbling argon for 1.5 hours at the temperature of 8-10 ℃, and then rectifying to obtain the deuterated trifluoroacetic acid.
The conversion of heavy water was calculated to be 98.5%.
Comparative example 1
A preparation method of deuterated trifluoroacetic acid comprises the following steps:
in comparison with example 3, the dehydration in step one was entirely replaced by phosphorus pentoxide, the rest being the same.
The conversion to heavy water was calculated to be 90.7%.
As can be seen from the values of the conversion rates of heavy water in examples 3 to 5 and comparative example 1, examples 3 to 5 provide a method for preparing deuterated trifluoroacetic acid that is superior to the method employed in comparative example 1.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. A preparation method of deuterated trifluoroacetic acid is characterized by comprising the following steps: the method comprises the following steps:
step one, soaking amino artificial zeolite in ammonium dihydrogen phosphate solution for 1-1.5h by adopting an isometric soaking method, carrying out suction filtration, washing, then drying, roasting for 4h, grinding and sieving to obtain a dehydrating agent;
step two, adding a solvent and a dehydrating agent into a dry reaction kettle, stirring for 20-30min, dropwise adding trifluoroacetic acid under the stirring state, heating for reflux reaction for 6-24h after complete dropwise addition, distilling at normal pressure, collecting front fraction at 40-50 ℃, and rectifying the obtained front fraction to obtain trifluoroacetic anhydride;
and step three, adding trifluoroacetic anhydride into a dry reaction kettle, introducing argon, forming argon bubbling, then dropwise adding heavy water at 0 +/-3 ℃, completely dropwise adding, bubbling argon at 0-10 ℃ for 1-1.5h, and rectifying to obtain the deuterated trifluoroacetic acid.
2. The method of claim 1, wherein the deuterated trifluoroacetic acid is prepared by: in the first step, the mass concentration of the ammonium dihydrogen phosphate solution is 25-45%.
3. The method of claim 1, wherein the deuterated trifluoroacetic acid is prepared by: in the first step, the drying temperature is 100-.
4. The method of claim 1, wherein the deuterated trifluoroacetic acid is prepared by: and in the second step, the feeding mass ratio of the dehydrating agent to the trifluoroacetic acid is 1: 2-5.
5. The method of claim 1, wherein the deuterated trifluoroacetic acid is prepared by: in the third step, the molar ratio of trifluoroacetic anhydride to heavy water is 1: 1.05-1.2.
6. The method of claim 1, wherein the deuterated trifluoroacetic acid is prepared by: the amino artificial zeolite is prepared by the following steps:
ultrasonically dispersing the artificial zeolite into absolute ethyl alcohol, then adding 3-aminopropyl trimethoxy silane, heating and refluxing for 1.5-2h, then cooling to room temperature, ultrafiltering, and drying to obtain the amino artificial zeolite.
7. The method of claim 6, wherein the deuterated trifluoroacetic acid is prepared by: the dosage ratio of the artificial zeolite, the absolute ethyl alcohol and the 3-aminopropyl trimethoxy silane is 1g to 5-6mL to 0.3-0.5 g.
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Cited By (1)
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| CN114790155A (en) * | 2022-04-20 | 2022-07-26 | 山东汉峰新材料科技有限公司 | Production process of deuterated trifluoromethanesulfonic acid |
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| DE102011076303A1 (en) * | 2011-05-23 | 2012-11-29 | Wacker Chemie Ag | New solid salt of organosilanol or its hydrolysis/condensation product or organosilanols together with their hydrolysis/condensation products with alkali cations useful for hydrophobing mineralic substrates, building material and fibers |
| CN104803839A (en) * | 2015-03-20 | 2015-07-29 | 浙江理工大学 | Method for preparing trifluoroacetic anhydride |
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- 2022-02-25 CN CN202210179171.XA patent/CN114349630A/en active Pending
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| US6221335B1 (en) * | 1994-03-25 | 2001-04-24 | Isotechnika, Inc. | Method of using deuterated calcium channel blockers |
| DE102011076303A1 (en) * | 2011-05-23 | 2012-11-29 | Wacker Chemie Ag | New solid salt of organosilanol or its hydrolysis/condensation product or organosilanols together with their hydrolysis/condensation products with alkali cations useful for hydrophobing mineralic substrates, building material and fibers |
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Non-Patent Citations (1)
| Title |
|---|
| SIOW K. CHIN ET AL.,: "The deuteration of acetanilides", 《JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS》, vol. 19, no. 9, pages 1057 - 1061 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114790155A (en) * | 2022-04-20 | 2022-07-26 | 山东汉峰新材料科技有限公司 | Production process of deuterated trifluoromethanesulfonic acid |
| CN114790155B (en) * | 2022-04-20 | 2023-11-17 | 山东汉峰新材料科技有限公司 | Production process of deuterated trifluoro methane sulfonic acid |
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