CN114790155A - Production process of deuterated trifluoromethanesulfonic acid - Google Patents
Production process of deuterated trifluoromethanesulfonic acid Download PDFInfo
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- CN114790155A CN114790155A CN202210417836.6A CN202210417836A CN114790155A CN 114790155 A CN114790155 A CN 114790155A CN 202210417836 A CN202210417836 A CN 202210417836A CN 114790155 A CN114790155 A CN 114790155A
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- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 139
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims abstract description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 10
- 238000005554 pickling Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
- 238000005481 NMR spectroscopy Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 229910052763 palladium Inorganic materials 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000005587 bubbling Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
- C07B59/001—Acyclic or carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/05—Isotopically modified compounds, e.g. labelled
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a production process of deuterated trifluoromethanesulfonic acid, which belongs to the technical field of fine chemical engineering, and is characterized in that deuterated trifluoromethanesulfonic acid is prepared by a process of dropping heavy water into trifluoromethanesulfonic anhydride, a catalyst is added in the preparation process, activated carbon is used as a carrier, the activated carbon is subjected to pickling treatment by hydrochloric acid, the pickling can reduce the content of ash loaded on the surface of the activated carbon, nitric acid is used for carrying out oxidation treatment on the activated carbon, the nitric acid can enlarge pores of the activated carbon originally, the specific surface area of the activated carbon is increased, the activated carbon is subjected to pickling treatment and oxidation treatment and then carries active substance metal palladium to prepare the catalyst, the catalyst is used for catalysis, the reaction rate of trifluoromethanesulfonic anhydride and heavy water can be effectively accelerated, the reaction time is shortened, the generation rate of deuterated trifluoromethanesulfonic acid is increased, meanwhile, argon is introduced in the production process to maintain an inert gas environment, argon bubbling is used for stirring the liquid phase reaction.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a production process of deuterated trifluoromethanesulfonic acid.
Background
The deuterated trifluoromethanesulfonic acid is a light yellow liquid and is usually used as a detection reagent for nuclear magnetic detection of polymers, the deuterated trifluoromethanesulfonic acid is obtained by hydrolysis of trifluoromethanesulfonic anhydride and heavy water, the trifluoromethanesulfonic anhydride and the heavy water hardly react at a temperature lower than normal temperature, slow hydrolysis occurs at the room temperature, and the generation rate of the deuterated trifluoromethanesulfonic acid can be increased under the condition of catalyst catalysis.
The palladium has strong capability of absorbing and permeating hydrogen, so the palladium is very suitable for manufacturing a catalyst for hydrogenation reaction, the metal palladium is carried on the activated carbon to be a common method for preparing the hydrogenation catalyst, the activated carbon used as a carrier is often loaded with various impurities on the surface and in gaps, so the specific surface area is reduced, the activated carbon needs to be reasonably treated at present, and the strength of the activated carbon carrier cannot be reduced while the high specific surface area is ensured.
Disclosure of Invention
The invention aims to provide a production process of deuterated trifluoromethanesulfonic acid, which is used for solving the problems in the background art.
The purpose of the invention can be realized by the following technical scheme:
a production process of deuterated trifluoromethanesulfonic acid comprises the following steps:
adding trifluoromethanesulfonic anhydride and a catalyst into a flask, adding heavy water in batches under the conditions of a 60 ℃ oil bath and magnetic stirring, violently stirring after dropwise adding the heavy water each time, adding a batch of heavy water again after the previous batch of heavy water disappears after reaction, keeping the input of argon during stirring, maintaining the inert environment of a reaction system, obtaining two-phase immiscible liquid in the flask before the reaction is finished, and enabling the liquid in the flask to become homogeneous after the reaction is finished.
And step two, detecting the reaction process through nuclear magnetic resonance, and rectifying a product after a signal peak of a reactant in a nuclear magnetic resonance spectrogram completely disappears to obtain the deuterated trifluoromethanesulfonic acid.
The dosage ratio of the total amount of the trifluoromethanesulfonic anhydride and the heavy water in the reaction process is 10 kg: 0.75 kg.
Further, the catalyst is prepared by the following steps:
step one, 100g of activated carbon is placed in a reaction bottle, 2-5% hydrochloric acid is poured into the reaction bottle until the activated carbon is immersed, the activated carbon is stirred for 1 hour under the condition of 80 ℃ water bath, then the activated carbon is filtered and washed, the activated carbon is pickled by the hydrochloric acid, then the activated carbon pickled by the hydrochloric acid is placed in a new reaction bottle, 5-20% nitric acid is poured into the new reaction bottle until the activated carbon is immersed, the activated carbon is stirred for 2 hours under the condition of 70 ℃ water bath, and then the activated carbon is filtered and washed.
And step two, placing the activated carbon subjected to acid washing and oxidation treatment in a drying box at 80-120 ℃ for pretreatment for 3-5h, dispersing the pretreated activated carbon in 500mL of water to form a dispersion liquid, measuring 50mL of 3% chloropalladic acid, slowly dropwise adding the chloropalladic acid into the dispersion liquid, stirring for 8-10h, carrying out suction filtration operation on the dispersion liquid dropwise added with the chloropalladic acid, washing filter residues to be neutral, placing the filter residues in a drying box at 60 ℃ for drying to constant weight, roasting for 2-4h at 180 ℃ and 200 ℃ under a nitrogen atmosphere, finally introducing hydrogen at 50-70 ℃ for reduction, and maintaining for 2-4h to obtain the catalyst.
The invention has the beneficial effects that:
the invention adopts the mode of dropping heavy water into trifluoromethanesulfonic anhydride to produce deuterated trifluoromethanesulfonic acid, and compared with the traditional method of dropping trifluoromethanesulfonic anhydride into heavy water, the method can reduce the use amount of heavy water.
Meanwhile, a catalyst is added in the reaction, the catalyst takes active carbon as a carrier, the active carbon is subjected to acid pickling treatment by hydrochloric acid, the acid pickling can reduce the content of ash (mainly oxides of sodium, magnesium, iron, calcium, aluminum and the like) loaded on the surface of the active carbon, the active carbon is subjected to oxidation treatment by nitric acid, the nitric acid can enlarge pores of the original pores of the active carbon, the surface area of the active carbon is increased, the active carbon is subjected to acid pickling and oxidation treatment and then carries active substance metal palladium to prepare the catalyst, and the catalyst is used for catalysis in the reaction process, so that the reaction rate of trifluoromethanesulfonic anhydride and heavy water can be effectively accelerated, the reaction time is shortened, and the generation rate of deuterated trifluoromethanesulfonic acid is increased.
And finally, argon is introduced in the production process, on one hand, the conventional effect of maintaining an inert gas environment is achieved, on the other hand, the argon is introduced into the reaction liquid, and the argon is bubbled to achieve the stirring effect of the liquid phase reaction, so that the reaction speed is further accelerated.
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
Preparing a catalyst, comprising the steps of:
step one, 100g of activated carbon is placed in a reaction bottle, 2% hydrochloric acid is poured into the reaction bottle until the activated carbon is immersed, the activated carbon is stirred for 1 hour under the condition of 80 ℃ water bath, then the activated carbon is filtered and washed with water, the activated carbon is pickled by hydrochloric acid, then the activated carbon pickled by hydrochloric acid is placed in a new reaction bottle, 5% nitric acid is poured into the new reaction bottle until the activated carbon is immersed, the activated carbon is stirred for 2 hours under the condition of 70 ℃ water bath, and then the activated carbon is filtered and washed with water.
Step two, placing the activated carbon subjected to acid washing and oxidation treatment in a drying oven at 80 ℃ for pretreatment for 3 hours, dispersing the pretreated activated carbon in 500mL of water to form a dispersion liquid, measuring 50mL of 3% chloropalladic acid, slowly and dropwise adding the chloropalladic acid into the dispersion liquid, stirring for 8 hours, carrying out suction filtration operation on the dispersion liquid in which the chloropalladic acid is dropwise added, washing filter residues to be neutral, placing the filter residues in a drying oven at 60 ℃ for drying to constant weight, roasting for 2 hours at 180 ℃ under the nitrogen atmosphere, finally introducing hydrogen at 50 ℃ for reduction, and maintaining for 2 hours to obtain the catalyst.
Example 2
Preparing a catalyst, comprising the steps of:
step one, 100g of activated carbon is placed in a reaction bottle, 3% hydrochloric acid is poured into the reaction bottle until the activated carbon is immersed, the reaction bottle is stirred for 1 hour under the condition of 80 ℃ water bath, then the reaction bottle is filtered and washed with water, the activated carbon is pickled by hydrochloric acid, then the activated carbon pickled by hydrochloric acid is placed in a new reaction bottle, 10% nitric acid is poured into the new reaction bottle until the activated carbon is immersed, the reaction bottle is stirred for 2 hours under the condition of 70 ℃ water bath, and then the reaction bottle is filtered and washed with water.
And step two, placing the activated carbon subjected to acid washing and oxidation treatment in a drying oven at 100 ℃ for pretreatment for 4 hours, dispersing the pretreated activated carbon in 500mL of water to form a dispersion liquid, measuring 50mL of 3% chloropalladic acid, slowly dropwise adding the chloropalladic acid into the dispersion liquid, stirring for 9 hours, carrying out suction filtration on the dispersion liquid dropwise added with the chloropalladic acid, washing filter residues to be neutral, placing the filter residues in a drying oven at 60 ℃ for drying to constant weight, roasting for 3 hours at 190 ℃ under the nitrogen atmosphere, finally introducing hydrogen at 60 ℃ for reduction, and maintaining for 3 hours to obtain the catalyst.
Example 3
Preparing a catalyst, comprising the steps of:
step one, 100g of activated carbon is placed in a reaction bottle, 5% hydrochloric acid is poured into the reaction bottle until the activated carbon is immersed, the activated carbon is stirred for 1 hour under the condition of 80 ℃ water bath, then the activated carbon is filtered and washed with water, the activated carbon is pickled with hydrochloric acid, then the activated carbon pickled with hydrochloric acid is placed in a new reaction bottle, 20% nitric acid is poured into the new reaction bottle until the activated carbon is immersed, the activated carbon is stirred for 2 hours under the condition of 70 ℃ water bath, and then the activated carbon is filtered and washed with water.
Step two, placing the activated carbon subjected to acid washing and oxidation treatment in a drying oven at 120 ℃ for pretreatment for 5 hours, dispersing the pretreated activated carbon in 500mL of water to form a dispersion liquid, measuring 50mL of 3% chloropalladic acid, slowly and dropwise adding the chloropalladic acid into the dispersion liquid, stirring for 10 hours, carrying out suction filtration operation on the dispersion liquid in which the chloropalladic acid is dropwise added, washing filter residues to be neutral, placing the filter residues in a drying oven at 60 ℃ for drying to constant weight, roasting for 4 hours at 200 ℃ under the nitrogen atmosphere, finally introducing hydrogen at 70 ℃ for reduction, and maintaining for 4 hours to obtain the catalyst.
Example 4
Deuterated trifluoromethanesulfonic acid comprising the following steps:
step one, adding 10kg of trifluoromethanesulfonic anhydride and 50g of the catalyst prepared in example 1 into a flask, adding heavy water in batches under the conditions of a 60 ℃ oil bath and magnetic stirring, wherein the amount of the added heavy water in each batch is 0.1kg, violently stirring after dropping the heavy water every time, adding a batch of heavy water again after the previous batch of heavy water disappears after reaction, keeping the input of argon during stirring, maintaining the inert environment of a reaction system, forming two-phase immiscible liquid in the flask before the reaction is finished, and enabling the liquid in the flask to become homogeneous after the reaction is finished.
And step two, detecting the reaction process through nuclear magnetic resonance, adding 0.75kg of heavy water in total, and after the signal peak of the reactant in the nuclear magnetic resonance spectrogram completely disappears, taking the product for rectification to obtain the deuterated trifluoromethanesulfonic acid.
Example 5
Deuterated trifluoromethanesulfonic acid comprising the following steps:
step one, adding 10kg of trifluoromethanesulfonic anhydride and 50g of the catalyst prepared in example 2 into a flask, adding heavy water in batches under the conditions of a 60 ℃ oil bath and magnetic stirring, wherein the amount of the added heavy water in each batch is 0.1kg, violently stirring after dropping the heavy water every time, adding a batch of heavy water again after the previous batch of heavy water disappears after reaction, keeping the input of argon during stirring, maintaining the inert environment of a reaction system, forming two-phase immiscible liquid in the flask before the reaction is finished, and enabling the liquid in the flask to become homogeneous after the reaction is finished.
And step two, detecting the reaction process through nuclear magnetic resonance, adding 0.75kg of heavy water in total, and after the signal peak of the reactant in the nuclear magnetic resonance spectrogram completely disappears, taking the product for rectification to obtain the deuterated trifluoromethanesulfonic acid.
Example 6
Deuterated trifluoromethanesulfonic acid comprising the steps of:
step one, adding 10kg of trifluoromethanesulfonic anhydride and 50g of the catalyst prepared in example 3 into a flask, adding heavy water in batches under the conditions of a 60 ℃ oil bath and magnetic stirring, wherein the amount of the heavy water added in each batch is 0.1kg, violently stirring after dropping the heavy water every time, adding a batch of heavy water again after the previous batch of heavy water is reacted and disappears, keeping the input of argon gas during stirring, maintaining the inert environment of a reaction system, forming two-phase immiscible liquid in the flask before the reaction is finished, and changing the liquid in the flask into homogeneous phase after the reaction is finished.
And step two, detecting the reaction process through nuclear magnetic resonance, adding 0.75kg of heavy water in total, and after the signal peak of the reactant in the nuclear magnetic resonance spectrogram completely disappears, taking the product for rectification to obtain the deuterated trifluoromethanesulfonic acid.
Comparative example 1: deuterated trifluoromethanesulfonic acid was prepared based on example 6 without using a catalyst and with the remaining steps and conditions being unchanged.
Comparative example 2: deuterated trifluoromethanesulfonic acid was prepared on the basis of example 6 without using the catalyst prepared in example 3 and using activated carbon which had not been subjected to an acid wash and oxidation treatment as a support, with the remaining steps and conditions remaining unchanged.
Examples 4 to 6, comparative example 1 and comparative example 2 were monitored, and the time taken for the reaction system to complete during the preparation was recorded, and the results are shown in table 1:
TABLE 1
| Item | Example 4 | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 |
| Reaction time/min | 125 | 112 | 105 | 205 | 159 |
As can be seen from table 1:
(1) the data for comparative example 4, example 5, example 6 and comparative example 1 can be obtained: the reaction rate of the system after adding the catalyst prepared in the example 1 to the example 3 is faster, and the catalyst prepared in the example 1 to the example 3 has obvious catalytic effect.
(2) Comparing the data of comparative example 1 and comparative example 2 gives: the catalytic effect of the catalyst prepared by taking the acid-washed and oxidized activated carbon as a carrier is remarkably improved, impurities in the activated carbon can be removed by hydrochloric acid and nitric acid treatment, meanwhile, impurity pits in the activated carbon are brought, the specific surface area of the activated carbon is increased, and the internal pore structure of the activated carbon is slightly changed.
(3) The data for comparative example 4, example 5, and example 6 can be: the change of the treatment concentration of the hydrochloric acid and the nitric acid has certain influence on the catalytic effect of the catalyst.
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 it will be appreciated by those skilled in the art that various modifications, additions and substitutions can be made to the embodiments described without departing from the scope of the invention as defined in the appended claims.
Claims (6)
1. A production process of deuterated trifluoromethanesulfonic acid is characterized in that: the method comprises the following steps:
the method comprises the following steps: placing activated carbon in a reaction bottle, pouring 2-5% hydrochloric acid into the reaction bottle until the activated carbon is immersed, stirring for 1h under the condition of 80 ℃ water bath, then filtering and washing with water, placing the activated carbon subjected to hydrochloric acid pickling in a new reaction bottle, pouring 5-20% nitric acid into the new reaction bottle until the activated carbon is immersed, stirring for 2h under the condition of 70 ℃ water bath, and then filtering and washing with water to obtain the activated carbon with high specific surface area;
step two: pretreating the activated carbon with high specific surface area, dispersing the pretreated activated carbon in water to form a dispersion liquid, measuring 3% chloropalladate, slowly dropwise adding the chloropalladate into the dispersion liquid, stirring for 8-10 hours, and carrying out suction filtration, washing, drying, roasting and reduction to obtain a catalyst;
step three: adding trifluoromethanesulfonic anhydride and a catalyst into a flask, adding heavy water in batches under the conditions of oil bath at 60 ℃ and magnetic stirring, keeping argon input during stirring, and rectifying a product to obtain the deuterated trifluoromethanesulfonic acid.
2. The process of claim 1, wherein the process comprises: in the third step, the dosage ratio of the total amount of the trifluoromethanesulfonic anhydride and the heavy water is 10 kg: 0.75 kg.
3. The process of claim 1, wherein the process comprises: detecting through nuclear magnetic resonance in the reaction process of the third step, and stopping the reaction when the signal peak of the reactant in the nuclear magnetic resonance spectrogram completely disappears.
4. The process of claim 1, wherein the process comprises: step two, pretreatment step: the activated carbon with high specific surface area is placed in a drying box at 80-120 ℃ for treatment for 3-5 h.
5. The process of claim 1, wherein the deuterated trifluoromethanesulfonic acid is produced by: roasting conditions in the second step: roasting at the temperature of 180-200 ℃ in the nitrogen atmosphere for 2-4 h; and (3) reducing conditions: introducing hydrogen, wherein the reduction temperature is 50-70 ℃, and the reduction time is 2-4 h.
6. The process of claim 1, wherein the deuterated trifluoromethanesulfonic acid is produced by: the using ratio of the activated carbon to the water to the chloropalladate is 100 g: 500 mL: 50 mL.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008066158A1 (en) * | 2006-12-01 | 2008-06-05 | Wako Pure Chemical Industries, Ltd. | Method for deuterating alkane |
| US20100331540A1 (en) * | 2008-02-01 | 2010-12-30 | Haruki Shimodaira | Method for producing compound having deuterated aromatic ring or heterocyclic ring |
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