CN108579792A - A kind of Co-LDH@NC catalyst and its application - Google Patents
A kind of Co-LDH@NC catalyst and its application Download PDFInfo
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- CN108579792A CN108579792A CN201810561184.7A CN201810561184A CN108579792A CN 108579792 A CN108579792 A CN 108579792A CN 201810561184 A CN201810561184 A CN 201810561184A CN 108579792 A CN108579792 A CN 108579792A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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Abstract
The invention discloses a kind of Co LDH@NC catalyst and its application, which can be catalyzed the reaction of N [3 aminopropyl, 2 hydroxyl ethyl sulfone] 4 nitrobenzamides and hydrazine hydrate with optimal conditions, have higher product yield.The lone pair electrons of N atoms can supply SP2 hydridization carbon skeleton delocalized pi-bond negative electrical charges in its CN shell of the Co LDH@NC catalyst of the present invention, simultaneously because the strong interaction between Co and support C N shells, the electronics in Co is caused to be shifted to carbon skeleton, the synergistic effect of the two enhances the electron transport property and chemical reactivity of catalyst.The metal active constituent of the Co LDH@NC catalyst of nucleocapsid is wrapped up and is protected by carbon nitrogen shell; strong interaction between the two makes it have higher stability; the reduction of nitro formamide is had good selectivity, so that the yield of midbody product aminobenzamide greatly improves.
Description
Technical field
The present invention relates to a kind of Co-LDH@NC catalyst and its applications, belong to chemical industry synthesis field.
Background technology
The structural formula of N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- aminobenzamides：
It is important dyestuff intermediate, improves N- [3- aminopropyl -2- hydroxyl second
Sulfuryl] -4- aminobenzamides yield shorten the reaction time, have great importance., select suitable catalyst by N-
[3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides and hydrazine hydrate catalytic reaction life reduction reaction are highly desirable.
Invention content
The purpose of the present invention is to provide a kind of Co-LDH@NC catalyst and its applications, and the catalyst is with optimal conditions
It can be catalyzed the reaction of N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides and hydrazine hydrate, there is higher product
Yield.
A kind of Co-LDH@NC method for preparing catalyst is as follows：
Step 1 weighs 0.2g Co（NO3）2·6H20 and 0.7g Zn（NO3）2·6H20 is scattered in 30ml methanol, and it is molten to be denoted as A
Liquid weighs 1.0g 2-methylimidazoles and is scattered in 10ml methanol, be denoted as B solution, A is poured into B, 24 are stood after stirring 15min
H, centrifugation, methanol wash 3 times, and 24 h of oven drying obtains purple powder ZnCoZIF；
Above-mentioned purple powder is transferred in porcelain boat by step 2, is put into tube furnace, and calcination under nitrogen atmosphere is warming up to 900
DEG C, 3h is kept the temperature, taking-up sample is cooled to room temperature, obtains black powder Co/NC；
Step 3 weighs 50mg Co/NC in the salpeter solution of 4mol/L, ultrasound reflux 90 min, centrifugation, massive laundering wash to
Solution is in neutrality, and 24 h of oven drying obtains black powder NC；
Step 4 weighs 40mg NC and is scattered in 3ml aqueous solutions, 30 min of ultrasound, is charged with 8ml methanol, ultrasound 30
Min continuously adds 0.3g Co（NO3）2·6H20 and 0.3g 2-methylimidazoles stir 10 min, stand 2h, centrifuge, wash,
Drying, obtains Co-LDH@NC catalyst.
A kind of Co-LDH@NC catalyst is in synthesizing N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- aminobenzamides
Application.
The synthesis condition is as follows：N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides and hydrazine hydrate
Reduction reaction occurs under the effect of the catalyst and obtains midbody product N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- amino
Benzamide.
Advantageous effect：The lone pair electrons of N atoms can supply SP2 in its CN shell of the Co-LDH@NC catalyst of the present invention
Hydridization carbon skeleton delocalized pi-bond negative electrical charge, simultaneously because the strong interaction between Co and support C N shells, leads to the electricity in Co
Son is shifted to carbon skeleton, and the synergistic effect of the two enhances the electron transport property and chemical reactivity of catalyst.Nucleocapsid
The metal active constituent of the Co-LDH NC catalyst of structure is wrapped up and is protected by carbon nitrogen shell, strong phase interaction between the two
With higher stability is made it have, the reduction of nitro formamide is had good selectivity, so that intermediate produces
The yield of object aminobenzamide greatly improves.
N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides and hydrazine hydrate are sent out under the effect of the catalyst
Midbody product N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- aminobenzamides are obtained by the reaction in original of surviving.
Specific implementation mode
Embodiment 1
Co-LDH@NC method for preparing catalyst is as follows：
Step 1 weighs 0.2g Co（NO3）2·6H20 and 0.7g Zn（NO3）2·6H20 is scattered in 30ml methanol, and it is molten to be denoted as A
Liquid weighs 1.0g 2-methylimidazoles and is scattered in 10ml methanol, be denoted as B solution, A is poured into B, 24 are stood after stirring 15min
H, centrifugation, methanol wash 3 times, and 24 h of oven drying obtains purple powder ZnCoZIF；
Above-mentioned purple powder is transferred in porcelain boat by step 2, is put into tube furnace, and calcination under nitrogen atmosphere is warming up to 900
DEG C, 3h is kept the temperature, taking-up sample is cooled to room temperature, obtains black powder Co/NC；
Step 3 weighs 50mg Co/NC in the salpeter solution of 4mol/L, ultrasound reflux 90 min, centrifugation, massive laundering wash to
Solution is in neutrality, and 24 h of oven drying obtains black powder NC；
Step 4 weighs 40mg NC and is scattered in 3ml aqueous solutions, 30 min of ultrasound, is charged with 8ml methanol, ultrasound 30
Min continuously adds 0.3g Co（NO3）2·6H20 and 0.3g 2-methylimidazoles stir 10 min, stand 2h, centrifuge, wash,
Drying, obtains Co-LDH@NC catalyst.
A kind of synthetic method of N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- aminobenzamides, this method include with
Lower step：
Step 1, under ice-water bath mechanical agitation, by 18.6g 4- nitrobenzoyl chlorides and 15.0g 3- aminopropyls -2-
Hydroxyethyl thioether is dissolved in 80 ml toluene, and 30ml chloroacetic chlorides 1h is slowly added dropwise；
Step 2 adjusts above-mentioned system pH=5 with glacial acetic acid, and 0.2g wolframic acids are added, are slowly added dropwise under room temperature mechanical stirring condition
30% hydrogen peroxide of 24ml concentration, 1h are added dropwise, and system are then warming up to 85 DEG C, insulated and stirred reacts 3h；
Step 3 stops stirring after reaction, is cooled to room temperature, and filters, and filter cake is with successively with a small amount of water, petroleum ether and ethyl alcohol
Washing, obtains N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides after drying；
100ml ethyl alcohol, 1,2- dichloroethanes mixed solvents is added in step 4 in 250ml three-necked flasks（1:1）, 15.8g is added
N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides, under 45 DEG C of magnetic agitations dissolving 2.9g Co- are then added
LDH@NC catalyst, is then warming up to 65 DEG C, and slowly dropwise addition hydrazine hydrate 24.0ml, 3h are added dropwise, and continues 65 DEG C of heat preservations and stirs
Mix 3h；
It is in water white transparency that step 5, reaction, which terminate solution, is filtered while hot, and filter cake is washed with a small amount of absolute ethyl alcohol, obtains clear solution,
It is cooled to room temperature, -4 DEG C of refrigerated overnights, filters, filter cake is recrystallized with absolute ethyl alcohol, obtains white intermediate N [3- aminopropyls -
2- hydroxyls ethyl sulfone] -4- aminobenzamides.
Embodiment 2
100ml ethyl alcohol, 1,2- dichloroethanes mixed solvents is added in step 4 in 250ml three-necked flasks（1:1）, 13.8g is added
N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides, under 45 DEG C of magnetic agitations dissolving 2.9g Co- are then added
LDH@NC catalyst, is then warming up to 65 DEG C, and slowly dropwise addition hydrazine hydrate 24.0ml, 3h are added dropwise, and continues 65 DEG C of heat preservations and stirs
Mix 3h；Remaining step is the same as embodiment 1.
Embodiment 3
100ml ethyl alcohol, 1,2- dichloroethanes mixed solvents is added in step 4 in 250ml three-necked flasks（1:1）, 11.8g is added
N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides, under 45 DEG C of magnetic agitations dissolving 2.9g Co- are then added
LDH@NC catalyst, is then warming up to 65 DEG C, and slowly dropwise addition hydrazine hydrate 24.0ml, 3h are added dropwise, and continues 65 DEG C of heat preservations and stirs
Mix 3h；Remaining step is the same as embodiment 1.
Embodiment 4
100ml ethyl alcohol, 1,2- dichloroethanes mixed solvents is added in step 4 in 250ml three-necked flasks（1:1）, 9.8g is added
N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides, under 45 DEG C of magnetic agitations dissolving 2.9g Co- are then added
LDH@NC catalyst, is then warming up to 65 DEG C, and slowly dropwise addition hydrazine hydrate 24.0ml, 3h are added dropwise, and continues 65 DEG C of heat preservations and stirs
Mix 3h；Remaining step is the same as embodiment 1.
Embodiment 5
100ml ethyl alcohol, 1,2- dichloroethanes mixed solvents is added in step 4 in 250ml three-necked flasks（1:1）, 7.8g is added
N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides, under 45 DEG C of magnetic agitations dissolving 2.9g Co- are then added
LDH@NC catalyst, is then warming up to 65 DEG C, and slowly dropwise addition hydrazine hydrate 24.0ml, 3h are added dropwise, and continues 65 DEG C of heat preservations and stirs
Mix 3h；Remaining step is the same as embodiment 1.
Embodiment 6
100ml ethyl alcohol, 1,2- dichloroethanes mixed solvents is added in step 4 in 250ml three-necked flasks（1:1）, 5.8g is added
N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides, under 45 DEG C of magnetic agitations dissolving 2.9g Co- are then added
LDH@NC catalyst, is then warming up to 65 DEG C, and slowly dropwise addition hydrazine hydrate 24.0ml, 3h are added dropwise, and continues 65 DEG C of heat preservations and stirs
Mix 3h；Remaining step is the same as embodiment 1.
Embodiment 7
100ml ethyl alcohol, 1,2- dichloroethanes mixed solvents is added in step 4 in 250ml three-necked flasks（1:1）, 15.8g is added
N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides, under 45 DEG C of magnetic agitations dissolving 2.9g Co- are then added
LDH@NC catalyst, is then warming up to 65 DEG C, and slowly dropwise addition hydrazine hydrate 20.0ml, 3h are added dropwise, and continues 65 DEG C of heat preservations and stirs
Mix 3h；Remaining step is the same as embodiment 1.
Embodiment 8
100ml ethyl alcohol, 1,2- dichloroethanes mixed solvents is added in step 4 in 250ml three-necked flasks（1:1）, 15.8g is added
N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides, under 45 DEG C of magnetic agitations dissolving 2.9g Co- are then added
LDH@NC catalyst, is then warming up to 65 DEG C, and slowly dropwise addition hydrazine hydrate 16.0ml, 3h are added dropwise, and continues 65 DEG C of heat preservations and stirs
Mix 3h；Remaining step is the same as embodiment 1.
Embodiment 9
100ml ethyl alcohol, 1,2- dichloroethanes mixed solvents is added in step 4 in 250ml three-necked flasks（1:1）, 15.8g is added
N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides, under 45 DEG C of magnetic agitations dissolving 2.9g Co- are then added
LDH@NC catalyst, is then warming up to 65 DEG C, and slowly dropwise addition hydrazine hydrate 12.0ml, 3h are added dropwise, and continues 65 DEG C of heat preservations and stirs
Mix 3h；Remaining step is the same as embodiment 1.
Embodiment 10
100ml ethyl alcohol, 1,2- dichloroethanes mixed solvents is added in step 4 in 250ml three-necked flasks（1:1）, 15.8g is added
N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides, under 45 DEG C of magnetic agitations dissolving 2.9g Co- are then added
LDH@NC catalyst, is then warming up to 65 DEG C, and slowly dropwise addition hydrazine hydrate 8.0ml, 3h are added dropwise, and continues 65 DEG C of insulated and stirreds
3h；Remaining step is the same as embodiment 1.
Reference examples 1
It is with 1 difference of embodiment：In the synthesis step 1 of intermediate, 4- nitrobenzoyl chlorides and 3- aminopropyl -2- hydroxyls
Ethyl thioether mass ratio is 6:1, remaining step is identical with embodiment 1.
Reference examples 2
It is with 1 difference of embodiment：In the synthesis step 1 of intermediate, 4- nitrobenzoyl chlorides and 3- aminopropyl -2- hydroxyls
Ethyl thioether mass ratio is 1:6, remaining step is identical with embodiment 1.
Reference examples 3
It is with 1 difference of embodiment：In the synthesis step 1 of catalyst, Co（NO3）2·6H20 and Zn（NO3）2·6H20 mass
Than being 1:1, remaining step is identical with embodiment 1.
Reference examples 4
It is with 1 difference of embodiment：In the synthesis step 1 of catalyst, Co（NO3）2·6H20 and Zn（NO3）2·6H20 mass
Than being 7:2, remaining step is identical with embodiment 1.
Reference examples 5
It is with 1 difference of embodiment：In the synthesis step 1 of catalyst, Co is not added（NO3）2·6H20, remaining step with
Embodiment 1 is identical.
Reference examples 6
It is with 1 difference of embodiment：In the synthesis step 1 of catalyst, Zn is not added（NO3）2·6H20, remaining step with
Embodiment 1 is identical.
Reference examples 7
It is with 1 difference of embodiment：In the synthesis step 3 of catalyst, 50mg Co/NC in the sulfuric acid solution of 4mol/L, remaining
Step is identical with embodiment 1.
Reference examples 8
It is with 1 difference of embodiment：In the synthesis step 3 of catalyst, 50mg Co/NC in the hydrochloric acid solution of 4mol/L,
Remaining step is identical with embodiment 1.
Reference examples 9
It is with 1 difference of embodiment：In the synthesis step 4 of catalyst, Co（NO3）2·6H20 and 2-methylimidazole mass ratio be
10:1, remaining step is identical with embodiment 1.
Reference examples 10
It is with 1 difference of embodiment：In the synthesis step 4 of catalyst, Co（NO3）2·6H20 and 2-methylimidazole mass ratio be
1:10, remaining step is identical with embodiment 1.
It is as shown in the table for reaction result under embodiment and reference examples different condition
| N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- aminobenzamides yield/% | |
| Embodiment 1 | 98.6 |
| Embodiment 2 | 94.3 |
| Embodiment 3 | 80.4 |
| Embodiment 4 | 71.5 |
| Embodiment 5 | 68.1 |
| Embodiment 6 | 62.4 |
| Embodiment 7 | 75.1 |
| Embodiment 8 | 81.1 |
| Embodiment 9 | 66.5 |
| Embodiment 10 | 72.6 |
| Reference examples 1 | 33.1 |
| Reference examples 2 | 39.3 |
| Reference examples 3 | 47.4 |
| Reference examples 4 | 38.2 |
| Reference examples 5 | 38.5 |
| Reference examples 6 | 50.1 |
| Reference examples 7 | 39.0 |
| Reference examples 8 | 44.3 |
| Reference examples 9 | 47.0 |
| Reference examples 10 | 50.1 |
The experimental results showed that catalyst is to N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides and hydrazine hydrate
Synthetic reaction has good catalytic effect, and in one timing of reaction condition, intermediate yield is higher, and catalytic performance is better, on the contrary
It is poorer；When N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- nitrobenzamides, hydrazine hydrate mass ratio are reasonable 1,2 ratios,
Synthetic effect is best, with embodiment 1 the difference lies in that embodiment 3 to embodiment 10 changes primary raw material N- [3- aminopropans respectively
Base -2- hydroxyls ethyl sulfone] -4- nitrobenzamides, hydrazine hydrate dosage and proportioning, have different shadows to the yield of synthetic product
It rings；Reference examples 1 to reference examples 24- nitrobenzoyl chlorides and 3- aminopropyl -2- hydroxyethyl thioether mass ratioes changes,
Other steps are identical, and product yield is caused to be substantially reduced, and illustrate the product shadow with comparison first step reaction of two kinds of raw materials
Sound is very big；Reference examples 3 are to 6 Co of reference examples（NO3）2·6H20 and Zn（NO3）2·6H20 dosage changes, and effect is still not
It is good, illustrate Co（NO3）2·6H20 and Zn（NO3）2·6H20 is the essential raw material of catalyst；Reference examples 7 to reference examples 8 are used
Sulfuric acid and hydrochloric acid replace nitric acid, are catalyzed the variation with obvious effects of reaction, illustrate that the modification of nitric acid is preferable to catalyst improvement；
Reference examples 9 are to 10 Co of reference examples（NO3）2·6H20 and 2-methylimidazole mass ratio change, catalyst configuration changes,
The conversion ratio and selectivity of reaction are very low, and reaction effect is obviously deteriorated, and product yield is not still high；Therefore urging using the present invention
Agent has excellent catalytic effect to the synthetic reaction of N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- aminobenzamides.
Claims (3)
1. a kind of Co-LDH@NC method for preparing catalyst is as follows：
Step 1 weighs 0.2g Co（NO3）2·6H20 and 0.7g Zn（NO3）2·6H20 is scattered in 30ml methanol, and it is molten to be denoted as A
Liquid weighs 1.0g 2-methylimidazoles and is scattered in 10ml methanol, be denoted as B solution, A is poured into B, 24 are stood after stirring 15min
H, centrifugation, methanol wash 3 times, and 24 h of oven drying obtains purple powder ZnCoZIF；
Above-mentioned purple powder is transferred in porcelain boat by step 2, is put into tube furnace, and calcination under nitrogen atmosphere is warming up to 900
DEG C, 3h is kept the temperature, taking-up sample is cooled to room temperature, obtains black powder Co/NC；
Step 3 weighs 50mg Co/NC in the salpeter solution of 4mol/L, ultrasound reflux 90 min, centrifugation, massive laundering wash to
Solution is in neutrality, and 24 h of oven drying obtains black powder NC；
Step 4 weighs 40mg NC and is scattered in 3ml aqueous solutions, 30 min of ultrasound, is charged with 8ml methanol, ultrasound 30
Min continuously adds 0.3g Co（NO3）2·6H20 and 0.3g 2-methylimidazoles stir 10 min, stand 2h, centrifuge, wash,
Drying, obtains Co-LDH@NC catalyst.
2. a kind of Co-LDH@NC catalyst is in synthesis N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -4- as described in claim 1
Application in aminobenzamide.
3. application according to claim 2, the synthesis condition is as follows：N- [3- aminopropyl -2- hydroxyls ethyl sulfone] -
4- nitrobenzamides and hydrazine hydrate occur reduction reaction and obtain midbody product N- [3- aminopropans under the effect of the catalyst
Base -2- hydroxyls ethyl sulfone] -4- aminobenzamides.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114944495A (en) * | 2022-04-21 | 2022-08-26 | 同济大学 | Bifunctional oxygen electrocatalyst with CoN/MnO double-active sites and preparation and application thereof |
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| CN114944495A (en) * | 2022-04-21 | 2022-08-26 | 同济大学 | Bifunctional oxygen electrocatalyst with CoN/MnO double-active sites and preparation and application thereof |
| CN114944495B (en) * | 2022-04-21 | 2023-09-26 | 同济大学 | Difunctional oxygen electrocatalyst with CoN/MnO double active sites and preparation and application thereof |
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