CN115591544A - Preparation and application of hydrogenolysis catalyst - Google Patents

Preparation and application of hydrogenolysis catalyst Download PDF

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CN115591544A
CN115591544A CN202110721650.5A CN202110721650A CN115591544A CN 115591544 A CN115591544 A CN 115591544A CN 202110721650 A CN202110721650 A CN 202110721650A CN 115591544 A CN115591544 A CN 115591544A
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catalyst
hydrogenolysis
palladium
oxide
reaction
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余正坤
王连弟
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Dalian Institute of Chemical Physics of CAS
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    • 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
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings

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Abstract

The invention discloses a preparation method and application of a hydrogenolysis catalyst, which mainly solve the problem of low efficiency of the traditional hydrogenolysis catalyst. The hydrogenolysis catalyst is prepared by taking palladium chloride as a raw material, loading palladium on a metal oxide or a metal oxide composite carrier, and neutralizing with alkali. The catalyst can catalyze the hydrogenolysis debenzylation reaction of Hexabenzylhexaazaisowurtzitane (HBIW) or Tetraacetyldibenzylazaisowurtzitane (TAIW), so that the hexabenzylhexaazaisowurtzitane or the Tetraacetyldibenzylazaisowurtzitane (TAIW) is efficiently converted into the tetraacetyldibenzylazaisowurtzitane or the tetraacetylazaisowurtzitane, the yield is more than 90 percent, and the purity of a crude product is more than 95 percent. The method has the advantages of easily available raw materials, simple and convenient operation, mild reaction conditions, high catalyst efficiency, good target product selectivity, high synthesis efficiency and the like, and the catalyst can be recycled and has industrial application prospect.

Description

Preparation and application of hydrogenolysis catalyst
Technical Field
The invention relates to preparation and application of a hydrogenolysis catalyst, in particular to a palladium hydroxide hydrogenolysis catalyst prepared by taking palladium chloride as a raw material, loading palladium on a metal oxide or a metal oxide composite carrier and neutralizing with alkali.
Technical Field
Benzyl is an important protecting group, and is commonly used for protecting functional groups such as amine or hydroxyl. The introduction of the benzyl group is easier, but its removal is relatively difficult. There are many methods for debenzylation, such as hydrogenolysis debenzylation, oxidative debenzylation, etc., and there are other debenzylation reagents used. The hydrogenolysis carried out in the presence of a catalyst to convert the benzyl group to toluene is most commonly used today and generally does not destroy the compound itself. The palladium metal has excellent hydrogen absorption performance and is the best catalyst for the hydrogenolysis debenzylation reaction.
Supported palladium catalysts, especially Pd (OH) on activated carbon 2 The catalyst has excellent catalytic activity on hydrogenolysis debenzylation reaction, and shows better catalytic activity on the removal of N-benzyl than Pd (0) catalyst, and certain debenzylation reaction which cannot be realized under Pd/C catalysis can also be used for removing (Synth. Commun.1990,20, 1209).
Hexanitrohexaazaisowurtzitane (HNIW, also known as CL-20) is a cage type polynitroamine compound with high energy, high density, high detonation pressure and high detonation velocity. The hydrogenolysis and debenzylation of Hexabenzylhexaazaisowurtzitane (HBIW) and Tetraacetyldibenzylazaisowurtzitane (TADB) are key steps in the synthesis of CL-20. Because the process needs to use a large amount of noble metal hydrogenolysis catalysts, the synthesis cost is high. Because the cage structure of HBIW is very unstable, the catalyst activity for its hydrogenolysis debenzylation reaction is more demanding. The common Pd/C catalyst can hardly meet the requirements, and most of HBIW hydrogenolysis debenzylation catalysts reported in the literature at present are Pd (OH) 2 C (proceedings of Hebei university of industry, 2005,34,85; energetic materials, 2014,22, 441). Albeit Pd (OH) 2 The use of the/C catalyst for N-benzyl removal has been advanced, but there are problems such as unsatisfactory hydrogenolysis efficiency, possibility of ignition in the presence of a solvent, etc. To solve Pd (OH) 2 The defects of the/C catalyst can obviously reduce the synthesis cost of CL-20, and the development of a novel hydrogenolysis catalyst is urgently needed.
Disclosure of Invention
Aiming at the defects of the existing hydrogenolysis catalyst and the characteristics of HBIW and TADB hydrogenolysis reaction, the invention provides preparation and application of a hydrogenolysis catalyst, and mainly solves the problem of low efficiency of the existing hydrogenolysis catalyst. The hydrogenolysis catalyst is prepared by loading palladium hydroxide on a metal oxide or oxide composite carrier based on the metal oxide or metal oxide composite carrier. Due to the strong interaction between the palladium hydroxide and the metal carrier, the catalyst can efficiently promote the hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW for short) or tetraacetyldibenzylazaisowurtzitane (TADB for short), has higher efficiency and more stable structure, can be recycled, and has industrial application prospect.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing a hydrogenolysis catalyst comprising the steps of:
dissolving palladium chloride in MCl aqueous solution by using the palladium chloride as a raw material, and reacting the palladium chloride with the MCl aqueous solution to form M 2 PdCl 4 Then adding metal oxide or metal oxide composite carrier for impregnation treatment, neutralizing with alkali until the pH of the reaction system is 9-14, reacting at 5-80 ℃ for 1-24h to prepare high-activity Pd (OH) 2 A hydrogenolysis catalyst; the MCl is hydrochloric acid or alkali metal chloride, wherein M is H, K or Na; the molar ratio of palladium chloride to MCl is 1.
Based on the technical scheme, the metal oxide carrier is one or more than two of magnesium oxide, aluminum oxide, titanium dioxide, ferric oxide, ferroferric oxide, zinc oxide, zirconium dioxide and cerium oxide; the metal oxide composite carrier is diatomite, montmorillonite, hydrotalcite, kaolin, activated clay, molecular sieve, etc.
Based on the above technical scheme, M 2 PdCl 4 The dipping temperature of the aqueous solution in the carrier is 5-60 ℃, and the dipping time is 0.5-24h.
Based on the technical scheme, the alkali is an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, the mass concentration of the alkali is 1-30%, and the molar ratio of the alkali to the metal palladium is 2.
Based on the technical scheme, the concentration of the metal palladium in the reaction system is 0.01-0.1mol/L, and the content of the metal palladium in the hydrogenolysis catalyst is 1-20%.
Based on the above technical scheme, the reaction atmosphere for preparing the hydrogenolysis catalyst is air, nitrogen or argon.
The hydrogenolysis catalyst can be applied to the hydrogenolysis debenzylation reaction of Hexabenzylhexaazaisowurtzitane (HBIW) or Tetraacetyldibenzylazaisowurtzitane (TADB) to efficiently convert the hexabenzylhexaazaisowurtzitane or the tetraacetyldibenzylazaisowurtzitane into the tetraacetyldibenzylazaisowurtzitane. When the hydrogenolysis catalyst is applied to the hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane, under the condition of lower hydrogenolysis catalyst dosage (Pd dosage is 0.3-0.8mol percent of HBIW), hexabenzylhexaazaisowurtzitane reacts with acetic anhydride under the action of hydrogen gas to generate hydrogenolysis debenzylation acetylation and conversion into tetraacetyldibenzylazaisowurtzitane;
when the hydrogenolysis catalyst is applied to the hydrogenolysis debenzylation reaction of tetraacetyldibenzylazaisowurtzitane, the tetraacetyldibenzylazaisowurtzitane reacts with acetic acid under the action of hydrogen under the condition of lower dosage of the hydrogenolysis catalyst (the dosage of Pd is 0.3-0.8mol percent of the dosage of TADB), and the tetraacetyldibenzyl azaisowurtzitane is converted into the tetraacetylazaisowurtzitane through hydrogenolysis debenzylation.
The invention has the following advantages: because of strong interaction between palladium hydroxide and a metal carrier, the catalyst is more stable, has higher activity in the hydrogenolysis debenzylation reaction, can efficiently catalyze the hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane or tetraacetyldibenzylazaisowurtzitane, and has the yield of more than 90 percent and the purity of a crude product of more than 95 percent. In addition, the preparation method of the hydrogenolysis catalyst has the advantages of easily available raw materials, simple and convenient operation, mild reaction conditions, high catalyst efficiency, good selectivity of target products, high yield and the like, and the catalyst can be recycled and has industrial application prospects.
Detailed Description
The method takes palladium chloride as a raw material, the palladium chloride is dissolved in MCl aqueous solution, and the palladium chloride reacts with the MCl aqueous solution to form M 2 PdCl 4 And then adding a metal oxide or a metal oxide composite carrier for impregnation treatment, and neutralizing with alkali to prepare the hydrogenolysis catalyst.
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
The starting hexabenzylhexaazaisowurtzitane HBIW was prepared according to the literature (J.org.chem.1990, 55, 1459); the starting tetraacetyldibenzylhexaazaisowurtzitane TADB was prepared according to the experimental procedure of example 17.
Example 1
Palladium chloride (60mg, 0.37mmol), potassium chloride (276 mg,3.7 mmol) and 10mL of water were charged into a 50mL single-neck flask with a branch port under a nitrogen atmosphere, stirred until the palladium chloride was completely dissolved, 338mg of titanium dioxide was added thereto, the flask was immersed at 30 ℃ for 3 hours, then a 10% aqueous sodium hydroxide solution (2.22mL, 5.55mmol) was added thereto at a pH of about 13.5, and after completion of the addition, the flask was reacted at 30 ℃ for 18 hours.
After the reaction, the reaction mixture was centrifuged, and the solid was washed with 2X 10mL of water and dried under vacuum to obtain 383mg of a brown solid hydrogenolysis catalyst in 98% yield with a palladium content of 9.7%.
Example 2
The reaction procedure is the same as that of example 1, except that MCl is hydrochloric acid (36% strength) (0.30mL, 2.96mmol) and the impregnation temperature is 5 ℃ under an argon atmosphere in example 1.
And (3) reaction results: 376mg of a brown solid hydrogenolysis catalyst was obtained in 96% yield with a palladium content of 9.8%.
Example 3
The reaction procedure was the same as that of example 1 except that MCl was sodium chloride (36%) (649 mg, 11.1mmol) and the impregnation time was 0.5h under an air atmosphere in example 1.
And (3) reaction results: 364mg of a brown solid hydrogenolysis catalyst in 93% yield and 9.9% palladium content.
Example 4
The reaction procedure and operation were the same as in example 1, except that the molar ratio of palladium chloride to potassium chloride was 1.
And (3) reaction results: 379mg of the brown solid hydrogenolysis catalyst, yield 97% and palladium content 9.8%.
Example 5
The reaction procedure was the same as example 1 except that the molar ratio of palladium chloride to potassium chloride was 1.
And (3) reaction results: 383mg of the brown solid hydrogenolysis catalyst was obtained in 98% yield with a palladium content of 9.9%.
Example 6
The procedure is as in example 1, except that 721mg of zirconium dioxide support and 5mL of water are added and the impregnation time is 8h, as in example 1.
And (3) reaction results: 758mg of a brown solid hydrogenolysis catalyst, 98% yield and 4.9% palladium content.
Example 7
The reaction procedure and operation were the same as example 1, except that 3.81g of γ -alumina carrier was added, the impregnation temperature was 50 ℃ and the impregnation time was 16 hours, compared with example 1.
And (3) reaction results: 3.70g of a brown solid hydrogenolysis catalyst, yield 97% and palladium content 0.98%.
Example 8
The procedure of reaction was the same as in example 1, except that 338mg of the magnesium oxide support was added, the impregnation temperature was 20 ℃ and the impregnation time was 10 hours, as in example 1.
And (3) reaction results: 383mg of the brown solid hydrogenolysis catalyst was obtained in 98% yield with a palladium content of 9.8%.
Example 9
The reaction procedure and operation were the same as in example 1, except that 338mg of cerium oxide support was added, the impregnation temperature was 25 ℃ and the impregnation time was 20 hours, respectively, from example 1.
And (3) reaction results: 383mg of the brown solid hydrogenolysis catalyst was obtained with a yield of 98% and a palladium content of 9.9%.
Example 10
The reaction steps and the operation are the same as example 1, and the difference from example 1 is that 338mg of montmorillonite K10 carrier is added, the impregnation temperature is 10 ℃, and the impregnation time is 24h.
And (3) reaction results: 379mg of the brown solid hydrogenolysis catalyst, yield 97% and palladium content 9.8%.
Example 11
The reaction procedure and operation were the same as in example 1, except that 141mg of the hydrotalcite support was added, the impregnation temperature was 40 ℃ and the impregnation time was 6 hours, respectively, from example 1.
And (3) reaction results: 187mg of the brown solid hydrogenolysis catalyst was obtained in 97% yield with a palladium content of 19.9%.
Example 12
The reaction procedure and operation are the same as example 1, except that 185mg of activated clay carrier is added, the impregnation temperature is 25 deg.C, and the impregnation time is 12h, as in example 1.
And (3) reaction results: 232mg of a brown solid hydrogenolysis catalyst was obtained with a yield of 98% and a palladium content of 14.8%.
Example 13
The procedure is as in example 1, except that the molar ratio of alkali to metallic palladium is 20.
And (3) reaction results: 379mg of the brown solid hydrogenolysis catalyst was obtained in 97% yield and 9.9% palladium content.
Example 14
The procedure is as in example 1, except that the molar ratio of base to metallic palladium is 8.
And (3) reaction results: 383mg of the brown solid hydrogenolysis catalyst was obtained with a yield of 98% and a palladium content of 9.9%.
Example 15
The procedure is as in example 1, except that 5% strength aqueous sodium carbonate (11.76mL, 5.55mmol) is added to the reaction, the pH is about 10.2, the reaction temperature is 70 ℃ and the reaction time is 24h.
And (3) reaction results: 379mg of the brown solid hydrogenolysis catalyst was obtained in 97% yield and 9.7% palladium content.
Example 16
The procedure is as in example 1, except that a 15% strength aqueous solution of potassium carbonate (5.11mL, 5.55mmol) is added to the reaction, the pH is about 11.9, the reaction temperature is 50 ℃ and the reaction time is 6h.
And (3) reaction results: 383mg of the brown solid hydrogenolysis catalyst was obtained in 98% yield with a palladium content of 9.8%.
Example 17
Figure BDA0003137039430000071
A200 mL reaction vessel was charged with Pd (OH) prepared in example 1 2 /TiO 2 Catalyst (53.8mg, pd content 9.7%, pd usage 0.5 mol%), 210 uL bromobenzene, HBIW (7.089g, 10mmol), 20mL dimethylformamide, 15mL acetic anhydride, hydrogen charging to 0.6MPa, 20-40 ℃ reaction for 20h.
After the reaction is finished, performing suction filtration, washing the solid with 2X 20mL of ethanol, dissolving the solid with dichloromethane, and concentrating the filtrate to obtain a white solid product TADB 4.753g, wherein the yield is 92% and the product purity is 97%. The target product is confirmed by nuclear magnetic resonance hydrogen spectrometry. 1 H NMR(400MHz,DMSO-d 6 )δ7.29-7.55(m,10H),6.12-6.62(m,2H),5.24-5.76(m,4H),3.95-4.37(m,4H),1.74-2.15(m,12H)。
Example 18
Figure BDA0003137039430000072
A200 mL reaction vessel was charged with Pd (OH) prepared in example 1 2 /TiO 2 Catalyst (53.8 mg, pd content 9.7%, pd usage 0.5 mol%), TADB (5.166g, 10mmol), 20mL acetic acid and 5mL water, charged with hydrogen gas to 0.5MPa, reacted at 50 ℃ in an oil bath for 20h.
After the reaction is finished, the catalyst is removed by suction filtration, the filtrate is subjected to vacuum removal of the solvent, 20mL of ethanol is added into the residue, and then suction filtration is carried out again, so that 3.263g of a white solid product TAIW is obtained, the yield is 97%, and the product purity is 98%. The target product is obtained by nuclear magnetic resonance hydrogen spectrum determinationAnd (5) confirming. 1 H NMR(400MHz,D 2 O)δ6.33-6.70(m,2H),5.57-5.68(m,4H),2.02-2.19(m,12H)。
Example 19
The procedure and operation are the same as in example 17, except that the catalyst is Pd (OH) prepared in example 7 2 A/gamma-alumina catalyst.
And (3) reaction results: the white solid product TADB 4.649g is obtained, the yield is 90 percent, and the product purity is 96 percent.
Example 20
The procedure and operation are the same as in example 17, except that the catalyst is Pd (OH) prepared in example 9 2 /CeO 2 A catalyst.
And (3) reaction results: the white solid product TADB 4.701g is obtained, the yield is 91 percent, and the product purity is 97 percent.
Example 21
The procedure and operation are the same as in example 17, except that the catalyst is Pd (OH) prepared in example 12 2 Active clay catalyst.
And (3) reaction results: the obtained white solid product TADB is 4.546g, the yield is 88 percent, and the product purity is 96 percent.
Example 22
The procedure and operation are the same as in example 18, except that the catalyst is Pd (OH) prepared in example 11 2 A hydrotalcite catalyst.
And (3) reaction results: the white solid product TAIW 3.195g is obtained, the yield is 95%, and the product purity is 97%.
Example 23
The procedure and operation are the same as in example 18, except that the catalyst is Pd (OH) prepared in example 8 2 a/MgO catalyst.
And (3) reaction results: the white solid product TAIW 3.162g is obtained, the yield is 94 percent, and the product purity is 97 percent.
Example 24
The reaction procedure and operation were the same as in example 17, except that the catalyst was the same as in example 1717 Pd (OH) recovered 2 /TiO 2 A catalyst.
And (3) reaction results: the white solid product TADB 4.494g is obtained, the yield is 87 percent and the product purity is 95 percent.
Example 25
The procedure and operation are the same as in example 18, except that the catalyst is Pd (OH) recovered in example 22 2 A hydrotalcite catalyst.
And (3) reaction results: the white solid product TAIW 3.061g with a yield of 91% and a product purity of 96% was obtained.

Claims (10)

1. A method for preparing a hydrogenolysis catalyst, comprising: the method comprises the following steps:
dissolving palladium chloride in MCl aqueous solution, adding metal oxide or metal oxide composite carrier for immersion treatment, neutralizing with alkali until the pH of a reaction system is 9-14, and reacting at 5-80 ℃ for 1-24h to obtain a palladium hydroxide hydrogenolysis catalyst;
wherein M is H, K or Na; the molar ratio of palladium chloride to MCl is 1.
2. The method of claim 1, wherein: the metal oxide carrier is one or more than two of magnesium oxide, aluminum oxide, titanium oxide, ferric oxide, ferroferric oxide, zinc oxide, zirconium oxide and cerium oxide, and the metal oxide composite carrier is diatomite, montmorillonite, hydrotalcite, kaolin, activated clay or molecular sieve.
3. The method of claim 1, wherein: the dipping temperature is 5-60 ℃, and the dipping time is 0.5-24h.
4. The method of claim 1, wherein: the alkali is an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, and the mass concentration of the alkali is 1-30%.
5. The method of claim 1, wherein: the molar ratio of alkali to metallic palladium is 2.
6. The method of claim 1, wherein: the concentration of the metal palladium in the reaction system is 0.01-0.1mol/L.
7. The method of claim 1, wherein: the reaction atmosphere is air, nitrogen or argon.
8. The method of claim 1, wherein: the palladium content in the hydrogenolysis catalyst is 1-20%.
9. Use of a hydrogenolysis catalyst according to any one of claims 1-8 in the hydrogenolysis debenzylation of hexabenzylhexaazaisowurtzitane or tetraacetyldibenzylazaisowurtzitane.
10. Use according to claim 9, wherein the amount of Pd used in the hydrogenolysis catalyst is 0.3 to 0.8mol% based on the amount of hexabenzylhexaazaisowurtzitane or tetraacetyldibenzylazaisowurtzitane.
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JP2013082637A (en) * 2011-10-06 2013-05-09 Ne Chemcat Corp Selective debenzylation method and selective hydrogenation catalyst used therein
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CN1571699A (en) * 2001-09-17 2005-01-26 恩格哈德公司 Improved precious metal catalyst for debenzylation
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