CN115160324A - Method for synthesizing TADB by HBIW hydrogenolysis debenzylation under catalysis of monoatomic palladium - Google Patents
Method for synthesizing TADB by HBIW hydrogenolysis debenzylation under catalysis of monoatomic palladium Download PDFInfo
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Abstract
The invention discloses a method for synthesizing TADB by catalyzing HBIW (HBIW) hydrogenolysis and debenzylation through monatomic palladium. The invention prepares the monoatomic palladium catalysts (Pd-SACs) and applies the catalysts to HBIW hydrogenolysis debenzylation synthesis TADB. Firstly, the monatomic palladium catalyst shows good catalytic effect due to the uniformity, coordination state, quantum confinement effect and the like of the monatomic catalyst. Secondly, the catalyst has stable structure and high dispersion of palladium, greatly reduces the dosage of noble metal palladium and has high utilization ratio to Pd atoms. Thirdly, the catalyst can catalyze the product TADB to be further hydrogenolyzed to synthesize TAIW. The method has the characteristics of low catalyst consumption and low palladium content in the catalyst, obviously improves the atom economy of the catalyst, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing TADB by catalyzing HBIW (HBIW hydrogenolysis and debenzylation) with monoatomic palladium.
Background
The synthesis of Tetraacetyldibenzylhexaazaisowurtzitane (TADB) by hydrogenolysis and debenzylation of Hexabenzylhexaazaisowurtzitane (HBIW) is a key step in the synthesis of hexanitrohexaazaisowurtzitane (CL-20). The reaction catalyst is still conventional Pd (OH) 2 The main factor of the production is/C, and the scarcity and high price of noble metal palladium directly increase the production cost. Therefore, recent work has been devoted to reducing the loading of the noble metal palladium to reduce the catalyst cost and to improve the activity, selectivity and stability of the metal nanoparticles. Patents CN111644194A, CN113210000A, CN112844439A and CN113731465A are respectively expressed in mpg-C 3 N 4 Carbon nitride (g-C) 3 N 4 NS), nitrogen-doped titanium dioxide and nitrogen-doped carbon nanotubes (N-CNTs) are used as carriers, a corresponding palladium catalyst is prepared, and HBIW is used for hydrogenolysis and debenzylation.
In recent years, a monatomic catalyst (SAC) having highly dispersed isolated atoms has been developed, which exhibits excellent catalytic activity and stability due to its uniformity, coordination state, quantum confinement effect, and the like when nano-sized metal particles are converted into a monatomic metal. The monatomic catalyst does not mean that a single zero-valent metal atom is an active center, the monatomic atom also has coordination effects such as electron transfer and the like with other atoms of the carrier, and often has certain charge property, and the synergistic effect of the metal atom and peripheral coordination atoms is a main reason of high activity of the catalyst. The atom utilization rate of the isolated metal sites is close to 100 percent, the atom efficiency can be greatly improved, and the metal centers are spatially isolated on the carrier and have great influence on the integral catalytic performance. Therefore, the TADB is synthesized by catalyzing HBIW hydrogenolysis and debenzylation by using the monoatomic palladium catalyst (Pd-SACs), and firstly, the monoatomic palladium catalyst shows a good catalytic effect; secondly, the catalyst has stable structure and high dispersion of palladium, thereby greatly reducing the dosage of noble metal palladium; thirdly, the catalyst can catalyze the product TADB to further synthesize Tetraacetylhexaazaisowurtzitane (TAIW) by hydrogenolysis. The method has the characteristics of low catalyst consumption and low palladium content in the catalyst, obviously improves the atom economy of the catalyst, and has good application prospect.
Disclosure of Invention
The invention aims to provide a method for synthesizing TADB by catalyzing HBIW (HBIW) hydrogenolysis debenzylation by using monatomic palladium catalyst.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
a method for synthesizing TADB by hydrogenolysis and debenzylation of monatomic palladium-catalyzed HBIW comprises the following steps:
the reaction raw materials are as follows: HBIW, monoatomic Palladium catalyst, ac 2 O, DMF and PhBr;
the reaction atmosphere is non-oxygen atmosphere;
the reaction temperature is as follows: controlling the reaction temperature of the first stage to be 10-30 ℃, reacting for 2-8 h, then raising the temperature, controlling the reaction temperature of the second stage to be 35-55 ℃, and reacting for 8-24 h;
after the reaction is finished, the product is filtered and washed to obtain the product TADB.
Optionally, the mass ratio of the HBIW to the monatomic palladium catalyst is 1 (0.01-0.1).
Optionally, the preparation method of the monatomic palladium catalyst comprises:
mixing the carrier, palladium salt and water uniformly, adjusting the pH to be 8-10, centrifugally drying, and reducing for 0.5-10 h at the temperature of 80-150 ℃ in a hydrogen atmosphere to obtain the monatomic palladium catalyst.
Optionally, the carrier is CeO 2 、Ni(OH) 2 、ZrO 2 And TiO 2 2 At least one of (a).
Optionally, the palladium salt is (NH) 4 ) 2 PdCl 6 Palladium nitrate, pd (C) 3 H 5 )(C 5 H 5 )、H 2 PdCl 4 、PdCl 2 And PdBr 2 At least one of。
Optionally, the mass fraction of Pd in the monatomic palladium catalyst in the total amount of the catalyst is 0.1% to 3%.
Optionally, the preparation method of the carrier comprises:
slowly dripping alkali solution into the metal salt solution, stirring for 10-120 min at room temperature, and then heating to 80-130 ℃ in a closed container, stirring and reacting for 10-24 h; after the reaction is finished, filtering, washing, drying or calcining to obtain the corresponding carrier.
Optionally, the metal salt is Ce (NO) 3 ) 3 ·6H 2 O、Ni(NO 3 ) 3 ·6H 2 O, zirconium n-propoxide, tetraisopropyl titanate and TiCl 4 At least one of (a).
Optionally, the alkali is NaOH, KOH or Na 2 CO 3 、NaHCO 3 And NH 4 At least one of OH.
Optionally, the non-oxygen atmosphere treatment method includes: the reactor was replaced at least three times with nitrogen and hydrogen, respectively.
The invention has the beneficial effects that:
(1) The TADB is synthesized by catalyzing HBIW (HBIW) hydrogenolysis debenzylation by using the monatomic palladium catalyst, and the monatomic palladium catalyst shows good catalytic effect due to the uniformity, coordination state, quantum confinement effect and the like of the monatomic catalyst.
(2) The monatomic palladium catalyst has stable structure and high dispersion of palladium, greatly reduces the dosage of noble metal palladium and has high utilization rate of Pd atoms.
(3) The product TADB is filtered without further purification, and the catalyst can catalyze the product TADB to further hydrogenize and synthesize TAIW.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following embodiments, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
The method for synthesizing TADB by hydrogenolysis and debenzylation of single-atom palladium-catalyzed HBIW comprises the following steps:
mixing HBIW, single atom palladium catalyst and Ac 2 O, DMF and PhBr were added to the reactor, and the reactor was replaced at least three times with nitrogen and hydrogen, respectively. Controlling the reaction temperature of the first stage to be 10-30 ℃, reacting for 2-8 h, then raising the temperature, controlling the reaction temperature of the second stage to be 35-55 ℃, and reacting for 8-24 h. After the reaction is finished, the product is filtered, washed and the like to obtain the product TADB.
According to the invention, the TADB is synthesized by catalyzing HBIW hydrogenolysis debenzylation by using the monatomic palladium catalyst, and the monatomic catalyst shows excellent catalytic activity and stability due to the uniformity, coordination state, quantum confinement effect and the like of the monatomic catalyst; the high dispersion of the palladium of the monatomic palladium catalyst greatly reduces the dosage of noble metal palladium, has high utilization rate of catalyst atoms and obviously improves the atom economy of the catalyst.
The mass ratio of HBIW to the monatomic palladium catalyst is 1.
The hydrogenolysis debenzylation reaction is shown as the following formula:
the preparation method of the monoatomic palladium catalyst comprises the following steps:
the carrier is placed in water to be stirred and treated by ultrasonic for 0.5 to 5 hours. Dissolving palladium salt in water, mixing the two solutions, stirring for 4-20 h, adjusting the pH = 8-10, and continuing stirring for 2-10 h. Centrifuging, drying, and reducing for 0.5-10 h at 80-150 ℃ in hydrogen atmosphere to obtain the monatomic palladium catalyst.
The carrier comprising CeO 2 、Ni(OH) 2 、ZrO 2 、TiO 2 One or a mixture of two or more of (1).
The palladium salt comprises (NH) 4 ) 2 PdCl 6 Palladium nitrate, pd (C) 3 H 5 )(C 5 H 5 )、H 2 PdCl 4 、PdCl 2 、PdBr 2 Or a mixture of two or more of them.
The mass fraction of Pd in the monatomic palladium catalyst is 0.1-3%.
The preparation method of the carrier comprises the following steps:
slowly dripping alkaline solution into the metal salt solution, stirring for 10-120 min at room temperature, and then heating to 80-130 ℃ in a closed container, stirring and reacting for 10-24 h. After the reaction is finished, filtering, washing, drying or calcining to obtain the corresponding carrier.
The metal salt comprises Ce (NO) 3 ) 3 ·6H 2 O、Ni(NO 3 ) 3 ·6H 2 O, zirconium n-propoxide, tetraisopropyl titanate, tiCl 4 One or a mixture of two or more of (1).
The alkali includes NaOH, KOH, na 2 CO 3 、NaHCO 3 、NH 4 One or a mixture of more than two OH.
The reaction temperature for preparing the carrier is 80-130 ℃, and the reaction time is 10-24 h.
The technical scheme of the invention is explained in detail by combining with specific examples, all experimental materials are commercially available, and the methods are common methods in the field if no special description is provided. Unless otherwise specified,% of the solution used hereinafter refers to mass percent concentration.
Example 1:
CeO 2 preparation of the carrier:
2.89g of Ce (NO) 3 ) 3 ·6H 2 Dissolving O in 40mL of water to prepare a metal salt solution, dissolving 0.05g of NaOH in 40mL of water to prepare an alkali solution, slowly dropwise adding the alkali solution into the metal salt solution, stirring at room temperature for 60min, transferring the reaction solution into a hydrothermal synthesis kettle, heating to 100 ℃, and stirring for reaction for 24h. Filtering, washing, drying at 60 ℃ for 5h, calcining at 400 ℃ for 4h after the reaction is finished to obtain CeO 2 And (3) a carrier.
1％Pd-CeO 2 Preparation of SACs catalyst:
0.1g of CeO 2 The support was placed in 20mL water with stirring andand (5) carrying out ultrasonic treatment for 1h. 3.5mg (NH) 4 ) 2 PdCl 6 Dissolve in 5mL water, mix the two solutions and stir for 12h, adjust pH =10, continue stirring for 5h. Centrifuging the reaction solution to obtain solid, drying at 40 deg.C for 2h, at 5% 2 /N 2 Reducing at 110 deg.C for 2h under hydrogen atmosphere to obtain 1% of Pd-CeO 2 SACs catalysts.
Synthesizing TADB by HBIW hydrogenolysis debenzylation:
1g of HBIW, 0.05g of 1% Pd-CeO 2 SACs catalyst, 3mL Ac 2 O, 5mL of DMF and 0.06g of PhBr were added to the reactor, and the reactor was replaced at least three times with nitrogen and hydrogen, respectively. Controlling the reaction temperature of the first stage to be 15 ℃, reacting for 4 hours, then raising the temperature, controlling the reaction temperature of the second stage to be 45 ℃, and reacting for 16 hours. After the reaction is finished, the product is filtered to obtain a crude product TADB (containing the catalyst), and the crude product TADB is further extracted, filtered and the like to obtain 0.642g of product TADB (the yield is 88%).
TADB hydrogenolysis synthesis of TAIW:
the reaction formula for the TADB hydrogenolysis reaction is as follows:
under a hydrogen atmosphere, 0.5g of the above crude product TADB (containing a catalyst), 2.4mL of acetic acid and 0.6mL of deionized water were sequentially added to a reactor under a reaction pressure of 0.4MPa at 50 ℃ for 20 hours, followed by filtration, rotary evaporation, crystallization and drying to obtain 0.299g of TAIW (yield 92%) as a product and 1% of Pd-CeO was recovered 2 SACs catalysts.
Example 2:
Ni(OH) 2 preparation of the carrier:
0.73g of Ni (NO) 3 ) 3 ·6H 2 Dissolving O in 10mL water to prepare metal salt solution, adding 0.3g urea, 0.8mL tetrabutyl ammonium hydroxide and 0.13g NaHCO 3 Dissolving in 10mL of water to prepare an alkali solution, slowly dropwise adding the alkali solution into the metal salt solution, stirring at room temperature for 10min, transferring the reaction solution into a hydrothermal synthesis kettle, heating to 120 ℃, and stirring for reaction for 24h. After the reaction is finished, filtering, washing, freeze-drying and drying for 24 hours to obtainTo Ni (OH) 2 And (3) a carrier.
0.5％Pd-Ni(OH) 2 Preparation of SACs catalyst:
0.1g of Ni (OH) 2 The support was stirred in 20mL of water and sonicated for 0.5h. 1mg of palladium nitrate was dissolved in 5mL of water, the two solutions were mixed and stirred for 20h, pH =9 was adjusted and stirring was continued for 10h. Centrifuging the reaction solution to obtain a solid, drying at 40 ℃ for 2h, at 10% 2 /N 2 Reducing under hydrogen atmosphere at 150 deg.C for 1h to obtain 0.5% Pd-Ni (OH) 2 SACs catalysts.
Synthesizing TADB by HBIW hydrogenolysis debenzylation:
1g of HBIW, 0.08g of 0.5% Pd-Ni (OH) 2 SACs catalyst, 3mL Ac 2 O, 5mL DMF and 0.06g PhBr were added to the reactor, and the reactor was replaced at least three times with nitrogen and hydrogen, respectively. Controlling the reaction temperature of the first stage to be 10 ℃, reacting for 8h, then raising the temperature, controlling the reaction temperature of the second stage to be 55 ℃, and reacting for 8h. After the reaction is completed, the product is filtered to obtain a crude product TADB (containing the catalyst), and the crude product TADB is further refined by extraction, filtration and the like to obtain 0.627g of product TADB (yield 86%).
Synthesizing TAIW by hydrogenolysis of TADB:
0.5g of the above crude product TADB (containing catalyst), 0.01g of 0.5% Pd-Ni (OH) under hydrogen atmosphere 2 SACs catalyst, 2.4mL acetic acid and 0.6mL deionized water were added to the reactor in sequence, the reaction pressure was 0.4Mpa, the reaction was carried out at 50 ℃ for 20 hours, and then after filtration, rotary evaporation, crystallization and drying, 0.303g of TAIW (93% yield) was obtained as a product and 0.5% Pd-Ni (OH) was recovered 2 SACs catalysts.
Example 3:
ZrO 2 preparation of the carrier:
dissolving 14.4mL of zirconium n-propoxide in 38mL of n-propanol to prepare a metal salt solution, 2 mL of 1% 4 And (3) adding an aqueous alkali into the metal salt solution slowly, dropwise adding the aqueous alkali into the metal salt solution, stirring at room temperature for 40min, transferring the reaction solution into a hydrothermal synthesis kettle, heating to 80 ℃, and stirring for reaction for 12h. Filtering, washing, drying at 60 ℃ for 5h, calcining at 400 ℃ for 4h after the reaction is finished to obtain ZrO 2 And (3) a carrier.
0.1％Pd-ZrO 2 Of SACs catalystsPreparation:
0.1g of ZrO was added 2 The support was stirred in 20mL water and sonicated for 3h. 0.2mg of Pd (C) 3 H 5 )(C 5 H 5 ) Dissolve in 5mL water, mix the two solutions and stir for 8h, adjust pH =10, continue stirring for 4h. Centrifuging the reaction solution to obtain a solid, drying at 40 ℃ for 2h, at 5% 2 /N 2 Reducing at 80 deg.C for 10h in hydrogen atmosphere to obtain 0.1% of Pd-ZrO 2 SACs catalysts.
Synthesizing TADB by HBIW hydrogenolysis debenzylation:
1g of HBIW, 0.10g of 0.1% Pd-ZrO 2 SACs catalyst, 3mL Ac 2 O, 5mL DMF and 0.06g PhBr were added to the reactor, and the reactor was replaced at least three times with nitrogen and hydrogen, respectively. Controlling the reaction temperature of the first stage at 30 ℃, reacting for 2 hours, then raising the temperature, controlling the reaction temperature of the second stage at 40 ℃, and reacting for 24 hours. After completion of the reaction, the product was filtered, washed, etc. to obtain 0.590g of a pure product TADB (yield 81%).
Example 4:
TiO 2 preparation of the carrier:
dissolving 1.42g of tetraisopropyl titanate in 80mL of ethanol to prepare a metal salt solution, dissolving 0.05g of KOH in 40mL of ethanol to prepare an alkali solution, slowly dropwise adding the alkali solution into the metal salt solution, stirring for 80min at room temperature, transferring the reaction solution into a hydrothermal synthesis kettle, heating to 90 ℃, and stirring for reacting for 16h. After the reaction is finished, filtering, washing, drying at 60 ℃ for 5h, calcining at 400 ℃ for 4h to obtain TiO 2 And (3) a carrier.
2％Pd-TiO 2 Preparation of SACs catalyst:
0.1g of TiO 2 The support was stirred in 20mL water and sonicated for 3h. 5.0mg of H 2 PdCl 4 Dissolve in 5mL water, mix the two solutions and stir for 4h, adjust pH =8, continue stirring for 10h. Centrifuging the reaction solution to obtain a solid, drying at 40 deg.C for 2h, at 50% H 2 /N 2 Reducing at 120 deg.C for 4h in hydrogen atmosphere to obtain 2% of Pd-TiO 2 SACs catalysts.
Synthesizing TADB by HBIW hydrogenolysis debenzylation:
mixing 1g HBIW and 0.04g2％Pd-TiO 2 SACs catalyst, 3mL Ac 2 O, 5mL of DMF and 0.06g of PhBr were added to the reactor, and the reactor was replaced at least three times with nitrogen and hydrogen, respectively. Controlling the reaction temperature of the first stage to be 15 ℃, reacting for 4 hours, then raising the temperature, controlling the reaction temperature of the second stage to be 35 ℃, and reacting for 24 hours. After the reaction is finished, the product is filtered to obtain a crude product TADB (containing the catalyst), and the crude product TADB is further extracted, filtered and the like to obtain 0.620g of the product TADB (yield is 85%).
TADB hydrogenolysis synthesis of TAIW:
0.5g of the above crude product TADB (containing a catalyst) and 0.005g of 2% by weight in a hydrogen atmosphere 2 Adding SACs catalyst, 2.4mL acetic acid and 0.6mL deionized water into a reactor in sequence, reacting at 50 deg.C for 20h under 0.4Mpa, filtering, rotary steaming, crystallizing, and drying to obtain 0.306g TAIW (yield 94%) and recovering 2% Pd-TiO 2 SACs catalysts.
Example 5:
TiO 2 preparation of the carrier:
1.89g of TiCl 4 Dissolving in 80mL water to obtain metal salt solution, adding 0.05g Na 2 CO 3 Dissolving in 80mL of water to prepare an alkali solution, slowly dropwise adding the alkali solution into the metal salt solution, stirring at room temperature for 120min, transferring the reaction solution into a hydrothermal synthesis kettle, heating to 130 ℃, and stirring for reaction for 10h. After the reaction is finished, filtering, washing, drying at 60 ℃ for 5h, calcining at 400 ℃ for 4h to obtain TiO 2 And (3) a carrier.
3％Pd-TiO 2 Preparation of SACs catalyst:
0.1g of TiO 2 The support was stirred in 20mL water and sonicated for 5h. 5.4mg of PdCl 2 Dissolve in 20mL water, mix the two solutions and stir for 8h, adjust pH =10, continue stirring for 2h. Centrifuging the reaction solution to obtain a solid, drying at 40 ℃ for 2h, at 5% 2 /N 2 Reducing at 150 deg.C for 0.5h under hydrogen atmosphere to obtain 3% Pd-TiO 2 SACs catalysts.
Synthesizing TADB by HBIW hydrogenolysis debenzylation:
1g of HBIW, 0.01g 3% Pd-TiO 2 SACs catalyst, 3mL Ac 2 O, 5mL DMF and 0.06g PhBr was added to the reactionIn the reactor, the reactor was replaced at least three times with nitrogen and hydrogen, respectively. Controlling the reaction temperature of the first stage to be 20 ℃, reacting for 4 hours, then raising the temperature, controlling the reaction temperature of the second stage to be 48 ℃, and reacting for 16 hours. After the reaction is completed, the product is filtered to obtain a crude product TADB (containing the catalyst), and the crude product TADB is further refined by extraction, filtration and the like to obtain 0.580g of the product TADB (yield 80%).
Synthesizing TAIW by hydrogenolysis of TADB:
under hydrogen atmosphere, 0.5g of the above crude TADB (containing catalyst), 2.4mL of acetic acid and 0.6mL of deionized water were sequentially added to a reactor, the reaction pressure was 0.4MPa, the reaction was carried out at 50 ℃ for 20 hours, and then, after filtration, rotary evaporation, crystallization and drying, 0.303g of TAIW (yield: 93%) was obtained as a product and 3% of Pd-TiO was recovered 2 SACs catalysts.
Example 6:
CeO 2 preparation of the carrier:
2.89g of Ce (NO) 3 ) 3 ·6H 2 Dissolving O in 40mL of water to prepare a metal salt solution, and dissolving 0.08g of NaHCO 3 Dissolving in 40mL of water to prepare an alkali solution, slowly dropwise adding the alkali solution into the metal salt solution, stirring at room temperature for 30min, transferring the reaction solution into a hydrothermal synthesis kettle, heating to 110 ℃, and stirring for reaction for 12h. Filtering, washing, drying at 60 ℃ for 5h, calcining at 400 ℃ for 4h after the reaction is finished to obtain CeO 2 And (3) a carrier.
0.6％Pd-CeO 2 Preparation of SACs catalyst:
0.1g of CeO 2 The support was stirred in 20mL water and sonicated for 2h. 1.6mg of PdBr 2 Dissolve in 5mL water, mix the two solutions and stir for 12h, adjust pH =10, continue stirring for 4h. Centrifuging the reaction solution to obtain solid, drying at 40 deg.C for 2h, at 5% 2 /N 2 Reducing at 120 deg.C for 2h in hydrogen atmosphere to obtain 0.6% of Pd-CeO 2 SACs catalysts.
Synthesizing TADB by HBIW hydrogenolysis debenzylation:
1g of HBIW, 0.02g of 0.6% of Pd-CeO 2 SACs catalyst, 3mL Ac 2 O, 5mL of DMF and 0.06g of PhBr were added to the reactor, and the reactor was replaced at least three times with nitrogen and hydrogen, respectively. Controlling the reaction temperature in the first stage at 18 deg.C, andthe temperature is increased for 6 hours, and then the reaction temperature in the second stage is controlled to be 43 ℃ for 24 hours. After the reaction is complete, the product is filtered, washed, etc. to yield 0.612g of the pure product TADB (81% yield).
The preferred embodiments of the present disclosure have been described above in detail, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. A method for synthesizing TADB by hydrogenolysis and debenzylation of single-atom palladium-catalyzed HBIW is characterized by comprising the following steps:
the reaction raw materials are as follows: HBIW, monoatomic Palladium catalyst, ac 2 O, DMF and PhBr;
the reaction atmosphere is non-oxygen atmosphere;
the reaction temperature is as follows: controlling the reaction temperature of the first stage to be 10-30 ℃, reacting for 2-8 h, then raising the temperature, controlling the reaction temperature of the second stage to be 35-55 ℃, and reacting for 8-24 h;
and after the reaction is finished, filtering and washing the product to obtain the product TADB.
2. The method for synthesizing TADB by the hydrogenolysis and debenzylation of the monatomic palladium-catalyzed HBIW according to claim 1, wherein the mass ratio of the HBIW to the monatomic palladium catalyst is 1 (0.01-0.1).
3. The method for synthesizing TADB by hydrogenolysis and debenzylation of HBIW catalyzed by monoatomic palladium according to claim 1 or 2, wherein the preparation method of the monoatomic palladium catalyst comprises the following steps:
mixing the carrier, palladium salt and water uniformly, adjusting the pH to be 8-10, centrifugally drying, and reducing for 0.5-10 h at the temperature of 80-150 ℃ in a hydrogen atmosphere to obtain the monatomic palladium catalyst.
4. The method for synthesizing TADB by the monoatomic palladium-catalyzed HBIW hydrogenolysis debenzylation according to claim 3, wherein the carrier is CeO 2 、Ni(OH) 2 、ZrO 2 And TiO 2 2 At least one of (a).
5. The method for synthesizing TADB by the monoatomic palladium-catalyzed HBIW hydrogenolysis debenzylation according to claim 3, wherein the palladium salt is (NH) 4 ) 2 PdCl 6 Palladium nitrate, pd (C) 3 H 5 )(C 5 H 5 )、H 2 PdCl 4 、PdCl 2 And PdBr 2 At least one of (1).
6. The method for synthesizing TADB by the hydrogenolysis and debenzylation of monatomic palladium-catalyzed HBIW according to claim 3, wherein the monatomic palladium catalyst comprises 0.1 to 3 percent of Pd by mass based on the total amount of the catalyst.
7. The method for synthesizing TADB by the hydrogenolysis and debenzylation of the monoatomic palladium-catalyzed HBIW according to claim 3, wherein the preparation method of the carrier comprises the following steps:
slowly dripping alkali solution into the metal salt solution, stirring for 10-120 min at room temperature, and then heating to 80-130 ℃ in a closed container, stirring and reacting for 10-24 h; after the reaction is finished, filtering, washing, drying or calcining to obtain the corresponding carrier.
8. The method for synthesizing TADB by hydrogenolysis and debenzylation of HBIW catalyzed by monoatomic palladium according to claim 7, wherein the metal salt is Ce (NO) 3 ) 3 ·6H 2 O、Ni(NO 3 ) 3 ·6H 2 O、Zirconium n-propoxide, tetraisopropyl titanate and TiCl 4 At least one of (a).
9. The method for synthesizing TADB by the monoatomic palladium-catalyzed HBIW hydrogenolysis debenzylation according to claim 7, wherein the base is NaOH, KOH or Na 2 CO 3 、NaHCO 3 And NH 4 At least one of OH.
10. The method for synthesizing TADB by hydrogenolysis and debenzylation of HBIW catalyzed by monoatomic palladium according to claim 1 or 2, wherein the treatment manner of the non-oxygen atmosphere comprises the following steps:
the reactor was replaced at least three times with nitrogen and hydrogen, respectively.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116116404A (en) * | 2023-04-19 | 2023-05-16 | 浙江工业大学 | Method for preparing hydrogenation catalyst by hydrothermal method and application of catalyst |
| CN116474812A (en) * | 2023-04-25 | 2023-07-25 | 天津大学 | Preparation method of catalyst for catalyzing VOCs oxidation |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6153749A (en) * | 1996-10-14 | 2000-11-28 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for the preparation of acylated hexaazaisowurtzitane derivatives |
| RU2448110C1 (en) * | 2010-10-21 | 2012-04-20 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Method for debenzylation of 2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazaisowurtzitane |
| US20130142720A1 (en) * | 2011-12-05 | 2013-06-06 | Industrial Technology Research Institute | The method of preparation of cerium oxide supported gold-palladium catalysts and its application in destruction of volatile organic compounds |
| CN106946894A (en) * | 2017-04-10 | 2017-07-14 | 中国科学院上海有机化学研究所 | Application of the Pd radicel duplex metal catalyst in HBIW catalytic hydrogenolytic cleavages |
| CN113731465A (en) * | 2021-08-31 | 2021-12-03 | 浙江工业大学 | Pd/N-CNTs catalyst, and preparation method and application thereof |
| CN113750993A (en) * | 2021-10-15 | 2021-12-07 | 中国科学院大连化学物理研究所 | Palladium monoatomic catalyst, preparation method thereof and application thereof in Suzuki coupling reaction |
| CN114456182A (en) * | 2021-12-27 | 2022-05-10 | 西安近代化学研究所 | Method for synthesizing TADB by HBIW hydrogenolysis debenzylation through acoustic resonance enhancement |
| CN114634513A (en) * | 2022-03-15 | 2022-06-17 | 西安近代化学研究所 | Method for synthesizing TADB by continuous hydrogenolysis and debenzylation of HBIW through acoustic resonance enhancement |
| CN114713265A (en) * | 2022-03-16 | 2022-07-08 | 西安近代化学研究所 | Method for preparing palladium-based catalyst through acoustic resonance enhancement and application |
| WO2022257025A1 (en) * | 2021-06-08 | 2022-12-15 | 中国科学院大连化学物理研究所 | Monatomically dispersed palladium-based catalyst, preparation method therefor and application thereof |
-
2022
- 2022-07-13 CN CN202210824754.3A patent/CN115160324A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6153749A (en) * | 1996-10-14 | 2000-11-28 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for the preparation of acylated hexaazaisowurtzitane derivatives |
| RU2448110C1 (en) * | 2010-10-21 | 2012-04-20 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Method for debenzylation of 2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazaisowurtzitane |
| US20130142720A1 (en) * | 2011-12-05 | 2013-06-06 | Industrial Technology Research Institute | The method of preparation of cerium oxide supported gold-palladium catalysts and its application in destruction of volatile organic compounds |
| CN106946894A (en) * | 2017-04-10 | 2017-07-14 | 中国科学院上海有机化学研究所 | Application of the Pd radicel duplex metal catalyst in HBIW catalytic hydrogenolytic cleavages |
| WO2022257025A1 (en) * | 2021-06-08 | 2022-12-15 | 中国科学院大连化学物理研究所 | Monatomically dispersed palladium-based catalyst, preparation method therefor and application thereof |
| CN113731465A (en) * | 2021-08-31 | 2021-12-03 | 浙江工业大学 | Pd/N-CNTs catalyst, and preparation method and application thereof |
| CN113750993A (en) * | 2021-10-15 | 2021-12-07 | 中国科学院大连化学物理研究所 | Palladium monoatomic catalyst, preparation method thereof and application thereof in Suzuki coupling reaction |
| CN114456182A (en) * | 2021-12-27 | 2022-05-10 | 西安近代化学研究所 | Method for synthesizing TADB by HBIW hydrogenolysis debenzylation through acoustic resonance enhancement |
| CN114634513A (en) * | 2022-03-15 | 2022-06-17 | 西安近代化学研究所 | Method for synthesizing TADB by continuous hydrogenolysis and debenzylation of HBIW through acoustic resonance enhancement |
| CN114713265A (en) * | 2022-03-16 | 2022-07-08 | 西安近代化学研究所 | Method for preparing palladium-based catalyst through acoustic resonance enhancement and application |
Non-Patent Citations (4)
| Title |
|---|
| SHUANG LIU ET AL.: "Stick-like mesoporous titania loaded Pd as highly active and cost effective catalysts for hydrodebenzylation of hexabenzylhexaazaisowurtzitane (HBIW)", 《MOLECULAR CATALYSIS》, pages 1 - 12 * |
| WEI ZHAO ET AL.: "Ultrasmall Pd Nanoparticles Supported on TiO2 for Catalytic Debenzylation via Hydrogenative C−N Bond Cleavage", 《ACS APPL. NANO MATER》, pages 159 - 166 * |
| 韩卫荣,欧育湘,陈博仁: "不同载体钯催化剂的结构表征及其在笼形叔胺脱N-苄基上的应用", 精细化工, no. 11 * |
| 鲍伶香等: "Pd( OH)2 /CeO2在六苄基六氮杂异伍兹烷和四乙酰基二苄基六氮杂异伍兹烷催化氢解脱苄反应中的应用", 《兵工学报》, pages 524 - 532 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116116404A (en) * | 2023-04-19 | 2023-05-16 | 浙江工业大学 | Method for preparing hydrogenation catalyst by hydrothermal method and application of catalyst |
| CN116474812A (en) * | 2023-04-25 | 2023-07-25 | 天津大学 | Preparation method of catalyst for catalyzing VOCs oxidation |
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