CN108772066A - A kind of catalyst and its application for synthesizing 3- aminopropyl -2- hydroxyethyl thioethers - Google Patents
A kind of catalyst and its application for synthesizing 3- aminopropyl -2- hydroxyethyl thioethers Download PDFInfo
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- CN108772066A CN108772066A CN201810470294.2A CN201810470294A CN108772066A CN 108772066 A CN108772066 A CN 108772066A CN 201810470294 A CN201810470294 A CN 201810470294A CN 108772066 A CN108772066 A CN 108772066A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- NOXAGGBPVGNKIW-UHFFFAOYSA-N 5-amino-1-(5-amino-2-hydroxypentyl)sulfanylpentan-2-ol Chemical class NCCCC(CSCC(CCCN)O)O NOXAGGBPVGNKIW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 29
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 17
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000011833 salt mixture Substances 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000004321 preservation Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- -1 adjusting pH= 10 Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- JZCBNVDLYZWNDB-UHFFFAOYSA-N 1-(2-hydroxypentylsulfanyl)pentan-2-ol Chemical class OC(CSCC(CCC)O)CCC JZCBNVDLYZWNDB-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical class OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 238000005732 thioetherification reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
- B01J23/007—Mixed salts
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of catalyst and its applications for synthesizing 3- aminopropyl -2- hydroxyethyl thioethers, the big specific surface area of this catalyst multilevel hierarchy, flourishing pore structure are conducive to the exposure of more adsorption activity positions, so that reaction can carry out rapidly and the multilevel hierarchy catalyst can magnetic recycling separation, to improve synthesis 3- aminopropyl -2- hydroxyethyl thioethers yield have the effect of it is excellent.
Description
Technical field
The present invention relates to a kind of catalyst and its applications for synthesizing 3- aminopropyl -2- hydroxyethyl thioethers, belong to
Chemical industry synthesis field.
Background technology
Sulphur is widely present in nature, is the important element for constituting life.Human use's sulphur or sulfur-containing compound have
Thousands of years history.With the development of modern science, sulfur-containing compound is on pesticide, medicine, chemical dyestuff and functional material
It suffers from and is widely applied very much.In organic compound, sulphur atom mostly exists with C-S keys, most commonly mercaptan and thioetherification
Close object.Thioether is concerned due to having important be widely applied on drug, dyestuff and new material.3- aminopropyls-
The structural formula of 2- hydroxyethyl thioethers：It is one kind of all polymorphic types of thioether, seeks one kind 5 and improve 2- ammonia
The catalyst of the synthetic yield of base -2- hydroxyls-diethyl thioether is highly desirable.
Invention content
The purpose of the present invention is to provide it is a kind of for synthesize 3- aminopropyl -2- hydroxyethyl thioethers catalyst and its
Using, the reaction of 3- mercaptoethanols and 3- propylamine hydrobromates can be catalyzed with optimal conditions, have higher product yield.
A kind of catalyst for synthesizing 3- aminopropyl -2- hydroxyethyl thioethers, which is characterized in that the catalysis
Agent is Fe3O4@MgAl-LDH catalyst.
The Fe3O4@MgAl-LDH method for preparing catalyst is as follows：
Step 1, by 0.232g Fe3O4Submicron particle ultrasonic disperse 20 minutes in 150ml methanol aqueous solutions, weigh 0.96g
NaOH and 0.636g Na2CO3It is 1 to be dissolved in volume ratio in 90ml methanol aqueous solutions:5, obtain mixed ammonium/alkali solutions；
Step 2 weighs 1.54g Mg（NO3）2·6H2O and 0.53g Al（NO3）3·9H2O is dissolved in 60ml methanol aqueous solutions,
Obtain mixing salt solution；
Mixed ammonium/alkali solutions are added dropwise to the Fe that above-mentioned ultrasound is crossed by step 33O4In submicron particle methanol aqueous solution, adjusting pH=
10, salt-mixture and mixed base is then added dropwise simultaneously with vigorous stirring, keeps pH=10, used time 1.5h；
Reaction vessel is transferred to 30 DEG C of 24 h of stirred in water bath crystallization by step 4, salt-mixture after dripping, after, magnetic sample
Respectively washing 3 times of separation, absolute ethyl alcohol and deionized water, then 60 DEG C of dry 12h roast 4h under 450 DEG C of air atmospheres, cooling
Fe is obtained to room temperature3O4@MgAl-LDH catalyst.
Catalyst as described in weighing 1 is in the application of synthesis 3- aminopropyl -2- hydroxyethyl thioethers, the synthesis 3- ammonia
The condition of base propyl -2- hydroxyethyl thioethers is：8.0g 3- mercaptoethanols are added in 250ml four-hole boiling flasks, room temperature magnetic force stirs
1.0g Fe are added under the conditions of mixing3O4@MgAl-LDH catalyst is slowly added dropwise 30% sodium hydroxide solution of 20mL concentration, drips
System is warming up to 50 DEG C after finishing, and 21.9g 3- propylamine hydrobromates 9ml water stirring and dissolvings are slowly added dropwise to above-mentioned reaction
In bottle, continue 50 DEG C of insulated and stirred 1h；
Stopping stirring after reaction, solution is in yellowish transparent, and bottom has a small amount of white solid to be precipitated, regulation system PH=10, on
50 DEG C of clarified solution of layer is spin-dried for obtaining thick liquid, with 50 DEG C of recrystallizations of absolute ethyl alcohol, obtains 12.4g light yellow viscous liquid products 3-
Aminopropyl -2- hydroxyethyl thioethers.
Advantageous effect：The present invention provides a kind of catalyst for synthesizing 3- aminopropyl -2- hydroxyethyl thioethers, adopt
It is prepared for the hud typed Fe of magnetic multilevel hierarchy with a step coprecipitation3O4@MgAl-LDH catalyst, stronger Molecular Adsorption energy
Power can be attributed to electrostatic attraction between the memory effect of shell MgFeAl-LDH, shell oxide and CR, hydrogen bond action, match
Position effect and the big specific surface area of multilevel hierarchy, flourishing pore structure are conducive to the exposure of more adsorption activity positions so that reaction
Can carry out rapidly and the multilevel hierarchy catalyst can magnetic recycling separation, to improve product yield have the effect of it is excellent.
Specific implementation mode
Embodiment 1
A kind of synthetic method of intermediate 3- aminopropyls -2- hydroxyethyl thioethers, includes the following steps：
8.0g 3- mercaptoethanols are added in step 1 in 250ml four-hole boiling flasks, and 1.0g is added under the conditions of room temperature magnetic agitation
Fe3O430% sodium hydroxide solution of 20mL concentration is slowly added dropwise in@MgAl-LDH catalyst, and rear system is added dropwise and is warming up to 50
DEG C, 21.9g 3- propylamine hydrobromates 9ml water stirring and dissolvings are slowly added dropwise into above-mentioned reaction bulb, continue 50 DEG C of guarantors
Temperature stirring 1h；
Step 2 stops stirring after reaction, and solution is in yellowish transparent, and bottom has a small amount of white solid to be precipitated, regulation system PH
=10,50 DEG C of supernatant liquid is spin-dried for obtaining thick liquid, with 50 DEG C of recrystallizations of absolute ethyl alcohol, obtains 12.4g light yellow viscous liquids
Product 3- aminopropyl -2- hydroxyethyl thioethers.
The Fe3O4@MgAl-LDH method for preparing catalyst is as follows：
Step 1, by 0.232g Fe3O4Submicron particle ultrasonic disperse 20 minutes in 150ml methanol aqueous solutions, weigh 0.96g
NaOH and 0.636g Na2CO3It is 1 to be dissolved in volume ratio in 90ml methanol aqueous solutions:5, obtain mixed ammonium/alkali solutions；
Step 2 weighs 1.54g Mg（NO3）2·6H2O and 0.53g Al（NO3）3·9H2O is dissolved in 60ml methanol aqueous solutions,
Obtain mixing salt solution；
Mixed ammonium/alkali solutions are added dropwise to the Fe that above-mentioned ultrasound is crossed by step 33O4In submicron particle methanol aqueous solution, adjusting pH=
10, salt-mixture and mixed base is then added dropwise simultaneously with vigorous stirring, keeps pH=10, used time 1.5h；
Reaction vessel is transferred to 30 DEG C of 24 h of stirred in water bath crystallization by step 4, salt-mixture after dripping, after, magnetic sample
Respectively washing 3 times of separation, absolute ethyl alcohol and deionized water, then 60 DEG C of dry 12h roast 4h under 450 DEG C of air atmospheres, cooling
Fe is obtained to room temperature3O4@MgAl-LDH catalyst.
Embodiment 2
6.0g 3- mercaptoethanols are added in step 1 in 250ml four-hole boiling flasks, and 1.0g is added under the conditions of room temperature magnetic agitation
Fe3O430% sodium hydroxide solution of 20mL concentration is slowly added dropwise in@MgAl-LDH catalyst, and rear system is added dropwise and is warming up to 50
DEG C, 21.9g 3- propylamine hydrobromates 9ml water stirring and dissolvings are slowly added dropwise into above-mentioned reaction bulb, continue 50 DEG C of guarantors
Temperature stirring 1h；Remaining step is the same as embodiment 1.
Embodiment 3
4.0g 3- mercaptoethanols are added in step 1 in 250ml four-hole boiling flasks, and 1.0g is added under the conditions of room temperature magnetic agitation
Fe3O430% sodium hydroxide solution of 20mL concentration is slowly added dropwise in@MgAl-LDH catalyst, and rear system is added dropwise and is warming up to 50
DEG C, 21.9g 3- propylamine hydrobromates 9ml water stirring and dissolvings are slowly added dropwise into above-mentioned reaction bulb, continue 50 DEG C of guarantors
Temperature stirring 1h；Remaining step is the same as embodiment 1.
Embodiment 4
2.0g 3- mercaptoethanols are added in step 1 in 250ml four-hole boiling flasks, and 1.0g is added under the conditions of room temperature magnetic agitation
Fe3O430% sodium hydroxide solution of 20mL concentration is slowly added dropwise in@MgAl-LDH catalyst, and rear system is added dropwise and is warming up to 50
DEG C, 21.9g 3- propylamine hydrobromates 9ml water stirring and dissolvings are slowly added dropwise into above-mentioned reaction bulb, continue 50 DEG C of guarantors
Temperature stirring 1h；Remaining step is the same as embodiment 1.
Embodiment 5
8.0g 3- mercaptoethanols are added in step 1 in 250ml four-hole boiling flasks, and 1.0g is added under the conditions of room temperature magnetic agitation
Fe3O430% sodium hydroxide solution of 20mL concentration is slowly added dropwise in@MgAl-LDH catalyst, and rear system is added dropwise and is warming up to 50
DEG C, 17.9g 3- propylamine hydrobromates 9ml water stirring and dissolvings are slowly added dropwise into above-mentioned reaction bulb, continue 50 DEG C of guarantors
Temperature stirring 1h；Remaining step is the same as embodiment 1.
Embodiment 6
8.0g 3- mercaptoethanols are added in step 1 in 250ml four-hole boiling flasks, and 1.0g is added under the conditions of room temperature magnetic agitation
Fe3O430% sodium hydroxide solution of 20mL concentration is slowly added dropwise in@MgAl-LDH catalyst, and rear system is added dropwise and is warming up to 50
DEG C, 15.9g 3- propylamine hydrobromates 9ml water stirring and dissolvings are slowly added dropwise into above-mentioned reaction bulb, continue 50 DEG C of guarantors
Temperature stirring 1h；Remaining step is the same as embodiment 1.
Embodiment 7
8.0g 3- mercaptoethanols are added in step 1 in 250ml four-hole boiling flasks, and 1.0g is added under the conditions of room temperature magnetic agitation
Fe3O430% sodium hydroxide solution of 20mL concentration is slowly added dropwise in@MgAl-LDH catalyst, and rear system is added dropwise and is warming up to 50
DEG C, 12.9g 3- propylamine hydrobromates 9ml water stirring and dissolvings are slowly added dropwise into above-mentioned reaction bulb, continue 50 DEG C of guarantors
Temperature stirring 1h；Remaining step is the same as embodiment 1.
Embodiment 8
8.0g 3- mercaptoethanols are added in step 1 in 250ml four-hole boiling flasks, and 1.0g is added under the conditions of room temperature magnetic agitation
Fe3O430% sodium hydroxide solution of 20mL concentration is slowly added dropwise in@MgAl-LDH catalyst, and rear system is added dropwise and is warming up to 50
DEG C, 9.9g 3- propylamine hydrobromates 9ml water stirring and dissolvings are slowly added dropwise into above-mentioned reaction bulb, continue 50 DEG C of heat preservations
Stir 1h；Remaining step is the same as embodiment 1.
Embodiment 9
8.0g 3- mercaptoethanols are added in step 1 in 250ml four-hole boiling flasks, and 1.0g is added under the conditions of room temperature magnetic agitation
Fe3O430% sodium hydroxide solution of 20mL concentration is slowly added dropwise in@MgAl-LDH catalyst, and rear system is added dropwise and is warming up to 50
DEG C, 6.9g 3- propylamine hydrobromates 9ml water stirring and dissolvings are slowly added dropwise into above-mentioned reaction bulb, continue 50 DEG C of heat preservations
Stir 1h；Remaining step is the same as embodiment 1.
Embodiment 10
8.0g 3- mercaptoethanols are added in step 1 in 250ml four-hole boiling flasks, and 1.0g is added under the conditions of room temperature magnetic agitation
Fe3O430% sodium hydroxide solution of 20mL concentration is slowly added dropwise in@MgAl-LDH catalyst, and rear system is added dropwise and is warming up to 50
DEG C, 3.9g 3- propylamine hydrobromates 9ml water stirring and dissolvings are slowly added dropwise into above-mentioned reaction bulb, continue 50 DEG C of heat preservations
Stir 1h；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, replace sodium hydroxide solution with the ammonium hydroxide of equivalent, remaining
Step is identical with embodiment 1.
Reference examples 2
It is with 1 difference of embodiment：In the synthesis step 1 of intermediate, sodium hydroxide solution is not added, remaining step and reality
It is identical to apply example 1.
Reference examples 3
It is with 1 difference of embodiment：In the synthesis step 1 of intermediate, with 10.g Fe3O4As catalyst, remaining step with
Embodiment 1 is identical.
Reference examples 4
It is with 1 difference of embodiment：In the synthesis step 1 of intermediate, catalyst is not added, remaining step and embodiment 1
It is identical.
Reference examples 5
It is with 1 difference of embodiment：In the synthesis step 2 of intermediate, regulation system PH=7, remaining step and embodiment 1 are complete
It is exactly the same.
Reference examples 6
It is with 1 difference of embodiment：In the synthesis step 2 of intermediate, regulation system PH=3, remaining step and embodiment 1 are complete
It is exactly the same.
Reference examples 7
It is with 1 difference of embodiment：In the synthesis step 1 of catalyst, NaOH, Na2CO3Mass ratio 5:1；Remaining step and reality
It is identical to apply example 1.
Reference examples 8
It is with 1 difference of embodiment：In the synthesis step 1 of catalyst, NaOH, Na2CO3Mass ratio 1:5；Remaining step and reality
It is identical to apply example 1.
Reference examples 9
It is with 1 difference of embodiment：In the synthesis step 2 of catalyst, Mg（NO3）2·6H2O, Al（NO3）3·9H2O mass
Than 1:1, remaining step is identical with embodiment 1.
Reference examples 10
It is with 1 difference of embodiment：In the synthesis step 2 of catalyst, Mg（NO3）2·6H2O, Al（NO3）3·9H2O mass
Than 1:3, remaining step is identical with embodiment 1.
It is as shown in the table for reaction result under embodiment and reference examples different condition
| 3- aminopropyl -2- hydroxyethyls thioethers yield/% | |
| Embodiment 1 | 99.8 |
| Embodiment 2 | 98.4 |
| Embodiment 3 | 74.8 |
| Embodiment 4 | 70.5 |
| Embodiment 5 | 87.1 |
| Embodiment 6 | 68.4 |
| Embodiment 7 | 83.0 |
| Embodiment 8 | 71.1 |
| Embodiment 9 | 69.5 |
| Embodiment 10 | 66.3 |
| Reference examples 1 | 59.1 |
| Reference examples 2 | 56.3 |
| Reference examples 3 | 47.0 |
| Reference examples 4 | 49.2 |
| Reference examples 5 | 55.5 |
| Reference examples 6 | 49.1 |
| Reference examples 7 | 42.2 |
| Reference examples 8 | 44.0 |
| Reference examples 9 | 56.7 |
| Reference examples 10 | 51.7 |
The experimental results showed that catalyst imitates the synthetic reaction of 3- mercaptoethanols and 3- propylamine hydrobromates with good catalysis
Fruit, in one timing of reaction condition, intermediate yield is higher, and catalytic performance is better, otherwise poorer；The 3- sulfydryl second of Examples 1 and 2
Synthetic effect is best when alcohol, 3- propylamine hydrobromate quality ratios, with embodiment 1 the difference lies in that embodiment 3 to embodiment 10 is divided
Not Gai Bian primary raw material 3- mercaptoethanols, 3- propylamine hydrobromates dosage and proportioning, have to the yield of synthetic product different
It influences；Reference examples 1 do not add sodium hydroxide solution to reference examples 2 and are replaced with ammonium hydroxide, other steps are identical, cause
Product yield is substantially reduced, and it is very big to illustrate that strong alkali environment influences reaction；Reference examples 3 to reference examples 6 use Fe3O4Make catalyst simultaneously
Reduction system pH value, effect is still bad, illustrates importance of the control to reaction of catalyst and system PH；Reference examples 7 are to right
8 NaOH, Na as usual2CO3Mass ratio changes, and is catalyzed the variation with obvious effects of reaction, illustrates that the proportioning of alkali source is also critically important；
Reference examples 9 to reference examples 10 change Mg（NO3）2·6H2O, Al（NO3）3·9H2O mass ratioes, catalyst structure change,
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 3- aminopropyl -2- hydroxyethyl thioethers.
Claims (3)
1. a kind of catalyst for synthesizing 3- aminopropyl -2- hydroxyethyl thioethers, which is characterized in that the catalyst
For Fe3O4@MgAl-LDH catalyst.
2. catalyst according to claim 1, which is characterized in that
The Fe3O4@MgAl-LDH method for preparing catalyst is as follows：
Step 1, by 0.232g Fe3O4Submicron particle ultrasonic disperse 20 minutes in 150ml methanol aqueous solutions, weigh 0.96g
NaOH and 0.636g Na2CO3It is 1 to be dissolved in volume ratio in 90ml methanol aqueous solutions:5, obtain mixed ammonium/alkali solutions；
Step 2 weighs 1.54g Mg（NO3）2·6H2O and 0.53g Al（NO3）3·9H2O is dissolved in 60ml methanol aqueous solutions,
Obtain mixing salt solution；
Mixed ammonium/alkali solutions are added dropwise to the Fe that above-mentioned ultrasound is crossed by step 33O4In submicron particle methanol aqueous solution, pH=10 are adjusted,
Then salt-mixture and mixed base is added dropwise simultaneously with vigorous stirring, keeps pH=10, used time 1.5h；
Reaction vessel is transferred to 30 DEG C of 24 h of stirred in water bath crystallization by step 4, salt-mixture after dripping, after, magnetic sample
Respectively washing 3 times of separation, absolute ethyl alcohol and deionized water, then 60 DEG C of dry 12h roast 4h under 450 DEG C of air atmospheres, cooling
Fe is obtained to room temperature3O4@MgAl-LDH catalyst.
3. the catalyst as described in power 1 is in the application for synthesizing 3- aminopropyl -2- hydroxyethyl thioethers, which is characterized in that described
The conditions of synthesis 3- aminopropyl -2- hydroxyethyl thioethers be：8.0g 3- mercaptoethanols are added in 250ml four-hole boiling flasks,
1.0g Fe are added under the conditions of room temperature magnetic agitation3O4It is molten that 30% sodium hydroxide of 20mL concentration is slowly added dropwise in@MgAl-LDH catalyst
Liquid is added dropwise rear system and is warming up to 50 DEG C, by 21.9g 3- propylamine hydrobromates 9ml water stirring and dissolvings, be slowly added dropwise to
In above-mentioned reaction bulb, continue 50 DEG C of insulated and stirred 1h；
Stopping stirring after reaction, solution is in yellowish transparent, and bottom has a small amount of white solid to be precipitated, regulation system PH=10, on
50 DEG C of clarified solution of layer is spin-dried for obtaining thick liquid, with 50 DEG C of recrystallizations of absolute ethyl alcohol, obtains 12.4g light yellow viscous liquid products 3-
Aminopropyl -2- hydroxyethyl thioethers.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4515337B2 (en) * | 2005-06-17 | 2010-07-28 | 千代田化工建設株式会社 | Porous titania for hydrotreating and hydrotreating method |
| CN102382706A (en) * | 2011-08-30 | 2012-03-21 | 华北电力大学 | Cavity structure TiO2 based Fe-based oxygen carrier and its preparation method |
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2018
- 2018-05-16 CN CN201810470294.2A patent/CN108772066A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4515337B2 (en) * | 2005-06-17 | 2010-07-28 | 千代田化工建設株式会社 | Porous titania for hydrotreating and hydrotreating method |
| CN102382706A (en) * | 2011-08-30 | 2012-03-21 | 华北电力大学 | Cavity structure TiO2 based Fe-based oxygen carrier and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| XIAOGE WU等: "Synthesis and adsorption properties of hierarchical Fe3O4@MgAl-LDH magnetic microspheres", 《J NANOPART RES》 * |
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