CN104624232A - Immobilized carbene catalyst, preparation method thereof, and method for preparing 1,3-dihydroxy acetone by using catalyst - Google Patents
Immobilized carbene catalyst, preparation method thereof, and method for preparing 1,3-dihydroxy acetone by using catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 33
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 18
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 18
- 238000009833 condensation Methods 0.000 claims abstract description 9
- 230000005494 condensation Effects 0.000 claims abstract description 9
- 239000004793 Polystyrene Substances 0.000 claims abstract description 4
- 229920002223 polystyrene Polymers 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000460 chlorine Substances 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 229920005990 polystyrene resin Polymers 0.000 claims description 6
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- GLISZRPOUBOZDL-UHFFFAOYSA-N 3-bromopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCBr GLISZRPOUBOZDL-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 230000008961 swelling Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 238000004458 analytical method Methods 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 238000013386 optimize process Methods 0.000 abstract description 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- FNXSZZYZBDFDDD-UHFFFAOYSA-N S1C=NC=C1.C(C)C1=CC=CC=C1 Chemical compound S1C=NC=C1.C(C)C1=CC=CC=C1 FNXSZZYZBDFDDD-UHFFFAOYSA-N 0.000 abstract 1
- 229940079593 drug Drugs 0.000 description 11
- 239000003814 drug Substances 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- IITIZHOBOIBGBW-UHFFFAOYSA-N 3-ethyl-2h-1,3-benzothiazole Chemical class C1=CC=C2N(CC)CSC2=C1 IITIZHOBOIBGBW-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- GIIOUWKWXHCKDV-UHFFFAOYSA-N 3-ethyl-2H-1,3-benzothiazole hydrobromide Chemical compound Br.C1=CC=C2N(CC)CSC2=C1 GIIOUWKWXHCKDV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 230000004151 fermentation Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000003622 immobilized catalyst Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 0 CC(*1)c2cc1c(CN(C)c1c(C)cccc1)cc2 Chemical compound CC(*1)c2cc1c(CN(C)c1c(C)cccc1)cc2 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000007976 Ketosis Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
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- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- ZQBVUULQVWCGDQ-UHFFFAOYSA-N propan-1-ol;propan-2-ol Chemical compound CCCO.CC(C)O ZQBVUULQVWCGDQ-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
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Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a carbene catalyst immobilized by silicon oxide or polystyrene, a preparation method thereof and a method for preparing 1,3-dihydroxy acetone by catalyzing formaldehyde condensation by using the catalyst. A halogen-containing bromized 3-ethyl benzene thiazolium and toxic and harmful triethylamine are not required in the analysis process of 1,3-dihydroxy acetone, the catalyst is convenient to separate and recover and can be used repeatedly. Under an optimized process condition, the conversion rate of paraformaldehyde is close to 100%, and the selectivity of 1,3-dihydroxy acetone is greater than 90%.
Description
Technical Field
The invention relates to an immobilized carbene catalyst, a preparation method thereof and a method for preparing 1, 3-dihydroxyacetone by using the catalyst, in particular to a carbene catalyst immobilized by silicon oxide or polystyrene, a preparation method thereof and a method for preparing 1, 3-dihydroxyacetone by using the catalyst to catalyze formaldehyde condensation.
Background
1, 3-dihydroxyacetone, DHA for short, is the simplest three-carbon ketose, is white or white-like powdery crystal in appearance, has sweet and cool taste, and is easy to absorb moisture and decompose. Generally, the monomer exists in a dimer form, can be slowly dissolved in 1 part of water or 15 parts of ethanol and is slightly soluble in ether, but becomes a monomer after being dissolved or heated, the monomer is easily soluble in organic solvents such as water or ethanol, the melting point is 75-80 ℃, the water solubility is more than 250g/L (20 ℃), and the monomer is stable when the pH is 6.0, and is an important fine chemical raw material, a medical intermediate and a multifunctional additive.
In the prior art, the production methods of 1, 3-dihydroxyacetone mainly comprise a formaldehyde condensation method, a microbial fermentation method and a glycerol oxidation method. The microbial fermentation method has long production period, low production efficiency and large waste liquid amount; the glycerol oxidation method has low product yield, the subsequent separation and extraction process is very complex due to the lower product concentration, the separation cost accounts for very high proportion of the total cost, and the method has no economic advantages. Compared with the two methods, the formaldehyde condensation method has the advantages of high product yield, low raw material cost and the like, and has obvious competitiveness in economy. As early as 1984, Toshihiko et al catalyzed formaldehyde condensation to prepare 1, 3-dihydroxyacetone from paraformaldehyde as a raw material, 3-ethylbenzothiazole bromide as a catalyst, and triethylamine as an auxiliary. When N, N-dimethylformamide is used as a solvent, the reaction yield is the highest, the conversion of paraformaldehyde is about 98%, and the selectivity of 1, 3-dihydroxyacetone is about 89% (J.Am.chem.Soc.,1984,106, 4829-4832). The preparation method of the 1, 3-dihydroxyacetone by using 3-ethylbenzothiazole bromide to catalyze formaldehyde to condense is characterized in that paraformaldehyde is used as a raw material, n-butanol is used as a solvent, triethylamine is used as a cocatalyst, the yield is about 37%, and the selectivity is 95-98% (fine chemical engineering, 2013,30(2), 225-plus 228).
Although the two methods have high selectivity for preparing 1, 3-dihydroxyacetone, in both methods, 3-ethylbenzothiazole salt and triethylamine are required to be added as a catalyst and a cocatalyst in the synthesis process of 1, 3-dihydroxyacetone, so that the operation is complex, the separation and recovery of the catalyst are difficult, and a plurality of halogen-containing byproducts are generated in the reaction process, thereby bringing great difficulty to the separation and purification of the subsequent products and finally influencing the quality of the products.
In order to solve the problems in the prior art, the invention takes paraformaldehyde as a raw material, and uses an immobilized carbene catalyst to catalyze formaldehyde for condensation to prepare the 1, 3-dihydroxyacetone. According to the invention, the brominated 3-ethylbenzothiazole salt containing halogen and toxic and harmful triethylamine are not used in the synthesis process of the 1, 3-dihydroxyacetone, and the catalyst is convenient to separate and recover and can be reused. Under the optimized process conditions, the conversion rate of paraformaldehyde is close to 100%, and the selectivity of 1, 3-dihydroxyacetone is more than 90%.
Disclosure of Invention
The invention aims to provide an immobilized carbene catalyst, a preparation method thereof and a method for preparing 1, 3-dihydroxyacetone by catalyzing formaldehyde condensation by using the catalyst.
According to one aspect of the present invention, the present invention provides an immobilized carbene catalyst, which has a structure of:
wherein n is the polymerization degree of the polystyrene carrier, and is an integer of 100-10000,represents a silica carrier.
According to another aspect of the present invention, the present invention provides a preparation method of the immobilized carbene catalyst, comprising the following steps:
a) selecting a chlorine ball with the crosslinking degree of 7 and the chlorine content of 12.8 percent as a carrier, swelling for 8-16 hours by using a mixed solvent of 1, 2-dichloroethane and ethanol, then adding benzothiazole into the chlorine ball according to the molar ratio of Cl contained in the chlorine ball to N contained in the benzothiazole of 1:1, carrying out reflux reaction for 8-16 hours, carrying out suction filtration, washing and extracting by using absolute ethyl alcohol to obtain the quaternized polystyrene resin;
wherein the proportion of the 1, 2-dichloroethane and the ethanol is not particularly limited, and the mass ratio of the 1, 2-dichloroethane and the ethanol is preferably 1: 0.1-100;
b) putting the quaternized polystyrene resin obtained in the step a) into a reaction kettle containing dioxane, adding triethylamine according to the molar ratio of Cl contained in chlorine spheres to N contained in triethylamine of 1:1, reacting for 16-28h at 373K under the protection of nitrogen, filtering under the protection of nitrogen, extracting with absolute ethyl alcohol, and drying in vacuum to obtain the polystyrene-immobilized carbene catalyst;
or,
a') mixing silicon dioxide and 20 wt% hydrochloric acid aqueous solution in a mass ratio of 1: 6-12, stirring and reacting for 3-6h at 373K, filtering, and drying to obtain activated silicon dioxide;
b ') mixing the activated silicon dioxide prepared in the step a') with anhydrous toluene and 3-bromopropyltrimethoxysilane according to the mass ratio of the silicon dioxide to the anhydrous toluene to the 3-bromopropyltrimethoxysilane of about 1: 10-20: 1, refluxing and reacting for 4-12h under stirring, washing with methanol after filtering, and drying in vacuum to obtain functionalized silicon dioxide;
c ') mixing the functionalized silicon dioxide prepared in the step b') with anhydrous toluene, adding benzothiazole according to the molar ratio of Br contained in the functionalized silicon dioxide to N contained in the benzothiazole of 1:1, refluxing and reacting for 18-30h under stirring, filtering, washing with methanol, and drying in vacuum to obtain silica-immobilized bromine salt;
d ') mixing the silica-immobilized bromine salt prepared in the step c') with dioxane, adding triethylamine according to the molar ratio of Br contained in the silica-immobilized bromine salt to N contained in the triethylamine of 1:1, stirring and reacting the mixture for 8-24 hours under the protection of nitrogen at 373K, filtering under the protection of nitrogen, extracting by using absolute ethyl alcohol, and drying in vacuum to obtain the silica-immobilized carbene catalyst.
Wherein the chlorine balls are commercially available, for example from Tianjin south-allowed high molecular technology, Inc.
The specific reaction is shown in the following reaction formula 1 or reaction formula 2:
reaction scheme 1
Reaction formula 2
According to another aspect of the present invention, there is provided a method for preparing 1, 3-dihydroxyacetone by formaldehyde condensation catalyzed by the above-mentioned immobilized carbene catalyst, which comprises the steps of:
adding paraformaldehyde, a solvent and the immobilized carbene catalyst into a reaction kettle respectively at room temperature, stirring, simultaneously heating to 100-150 ℃, and reacting for 0.5-5 h under the protection of nitrogen to obtain a product.
The solvent may be ethanol, isopropanol, 1, 4-dioxane, 1, 3-dioxolane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, or a mixture thereof, preferably isopropanol, N-dimethylacetamide, 1, 3-dioxolane, dimethylsulfoxide, or a mixture thereof.
The dosage of the solvent is 2-10 times of the mass of the paraformaldehyde.
The dosage of the immobilized carbene catalyst is 0.1-2 times of the mass of paraformaldehyde, preferably 0.1-0.4 times, more preferably 0.15-0.35 times, and more preferably 0.22-0.3 times.
The reaction temperature is 100-150 ℃, preferably 140-150 ℃; the reaction time is 0.5 to 5 hours, preferably 1 to 4 hours, and more preferably 2 to 4 hours.
After the reaction is finished, the reaction solution is simply filtered to separate and recover the catalyst, and the obtained 1, 3-dihydroxyacetone solution is directly subjected to liquid chromatography analysis.
The advantages of the invention include: 1. in the synthesis process of the 1, 3-dihydroxyacetone, the brominated 3-ethylbenzothiazole salt containing halogen and toxic and harmful triethylamine are not used, the product is easy to separate and purify, and the product quality is good; 2. the immobilized carbene catalyst used in the invention has good catalytic activity, the single-pass yield of the 1, 3-dihydroxyacetone is high, and the catalyst is convenient to separate and recover and can be reused.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of DHA prepared according to example 3 of the present invention;
fig. 2 is a nuclear magnetic resonance carbon spectrum of DHA prepared according to example 3 of the present invention.
Detailed Description
The invention is illustrated below with reference to specific examples. Those skilled in the art will appreciate that these examples are for illustrative purposes only and do not limit the scope of the present invention in any way.
In the examples, the sources of the raw materials are as follows: chlorine ball, Tianjin south-allowed high molecular technology, Inc.; 1, 2-dichloroethane, Beijing chemical Co., Ltd; absolute ethanol, beijing chemical agents ltd, national drug group; benzothiazole, Beijing chemical reagents, Inc., national drug group; triethylamine, Beijing chemical reagents, Inc., national drug group; silicon dioxide, Beijing chemical reagents, Inc., of the national drug group; hydrochloric acid, Beijing chemical reagents, Inc., of the national drug group; anhydrous toluene, Beijing chemical reagents, Inc., national drug group; paraformaldehyde, Beijing chemical reagents, Inc., national drug group; anhydrous methanol, beijing chemical reagents ltd, national drug group; dioxane, Beijing chemical reagents, Inc., of the national drug group; isopropyl alcohol, Beijing chemical reagents, Inc., national drug group; n, N-dimethylacetamide; beijing chemical reagents, Inc., national drug group; dimethyl sulfoxide, Beijing chemical Co., Ltd.
Example 1
40g of chlorine balls were weighed, and swollen overnight with 500mL of a mixed solvent of 1, 2-dichloroethane and 200mL of ethanol as a swelling agent, the next day in accordance with the Cl: adding benzothiazole into benzothiazole according to the mol ratio of N contained in the benzothiazole of 1:1, carrying out reflux reaction for 12 hours, carrying out suction filtration, washing, and then extracting for 12 hours by using absolute ethyl alcohol to obtain the brown yellow quaternized polystyrene resin.
The resulting quaternized polystyrene resin was placed in a 500mL reactor containing 250mL of dioxane, the molar ratio of Cl: triethylamine was added in a molar ratio of N contained in the triethylamine of 1:1 and the mixture was stirred under nitrogen for reaction at 373K for 24 h. And after the reaction is finished, filtering under the protection of nitrogen, extracting the filter cake for 10 hours by using 500mL of absolute ethyl alcohol, and drying in vacuum to obtain the immobilized carbene catalyst.
Example 2
50g of silica was weighed into a 500mL three-necked flask, and 300mL of 20% aqueous hydrochloric acid was added thereto, and the reaction was stirred at 373K for 4 hours. Then, the activated silica carrier is obtained by filtration and drying. And (3) putting the activated silicon dioxide into a 1L four-neck flask, adding 400mL of anhydrous toluene and 50mL of 3-bromopropyltrimethoxysilane, heating and refluxing for reaction for 10h under mechanical stirring, filtering, washing for 3 times by using 300mL of methanol, and drying in vacuum to obtain the functionalized silicon dioxide. The bromine atom content was 11.6% by Flohard method.
The resulting functionalized silica was charged into a 1L four-necked flask, 300mL of anhydrous toluene was added, and the ratio of Br contained in the functionalized silica: benzothiazole is added into the benzothiazole according to the mol ratio of 1:1, the reflux reaction is carried out for 18h under the mechanical stirring, after the filtration, methanol with 300mL is used for washing for 3 times, and after the vacuum drying, the bromine salt immobilized on silicon dioxide is obtained.
The silica-supported bromine salt thus obtained was put into a 1L reaction vessel containing 500mL of dioxane, and the molar ratio of Br contained in the silica-supported bromine salt was determined in accordance with the molar ratio of Br: triethylamine was added to the triethylamine in a molar ratio of N to 1, and the mixture was stirred under nitrogen at 373k for 12 h. And after the reaction is finished, filtering under the protection of nitrogen, extracting the filter cake for 10 hours by using 500mL of absolute ethyl alcohol, and drying in vacuum to obtain the immobilized carbene catalyst.
Example 3
9.01g of paraformaldehyde, 90mL of 1, 3-dioxolane and 2.53g of the immobilized carbene catalyst obtained in example 1 were added to a 150mL reaction vessel at room temperature, respectively, and the mixture was stirred mechanically with a strong force while the temperature was programmed to 140 ℃ and reacted for 2.0 hours under the protection of nitrogen. After the reaction is finished, the reaction solution is filtered, separated and recycled to obtain the 1, 3-dihydroxyacetone solution which is directly subjected to high performance liquid chromatography analysis. The conversion of paraformaldehyde is close to 100% and the selectivity of 1, 3-dihydroxyacetone is 92.37%.
The nuclear magnetic spectrum of 1, 3-dihydroxyacetone obtained according to this example is shown in FIGS. 1 and 2.
As shown in figure 1 of the drawings, in which,1h NMR spectrum (500MHz, D)2O), the group peak between 4.5 and 5.0 is the solvent peak, the peak between 4.0 and 4.5 is the H peak on methylene-CH 2, the peak between 3.0 and 3.5 is the H peak on-OH, the area ratio of the two peaks is about 2, and the number ratio of H on-CH 2 to H on-OH is satisfied.
As shown in figure 2 of the drawings, in which,13c NMR spectrum (500MHz, D)2O), the peak near 212 is the absorption peak of unsaturated C on carbonyl, the peak near 64 corresponds to the saturated C peak on methylene-CH 2, and the nuclear magnetic carbon spectrum of the product also proves that the product obtained by crystallization has a structure consistent with that of DHA.
Example 4
The reaction was carried out under the same conditions as in example 3 except that the catalyst obtained in example 2 was used in place of the catalyst obtained in example 1 used in example 3, and the analysis results showed that the conversion of paraformaldehyde was close to 100% and the selectivity of 1, 3-dihydroxyacetone was 95.01%.
Examples 5 to 7
1, 3-dihydroxyacetone was prepared in the same manner as in example 3, except that the catalyst amounts listed in Table 1 below were used, and the specific experimental results thereof are shown in Table 1.
TABLE 1
| Name of the embodiment | Amount of immobilized catalyst | Conversion rate% | Selectivity% |
| Example 5 | 1.51g | 89.04 | 90.16 |
| Example 6 | 2.05g | 96.75 | 92.93 |
| Example 7 | 3.01g | ≈100 | 88.42 |
Examples 8 to 10
1, 3-dihydroxyacetone was prepared in the same manner as in example 3, except that the reaction times shown in Table 2 below were used, and the results of the specific experiments thereof are shown in Table 2.
TABLE 2
| Name of the embodiment | Reaction time | Conversion rate% | Selectivity% |
| Example 8 | 1.0h | 72.54 | 90.62 |
| Example 9 | 3.0h | ≈100 | 93.08 |
| Example 10 | 4.0h | ≈100 | 85.11 |
Examples 11 to 23
1, 3-dihydroxyacetone was prepared in the same manner as in example 3, except that the reaction temperature in Table 3 below was used, and the specific experimental results thereof are shown in Table 3.
TABLE 3
| Name of the embodiment | Reaction temperature of | Conversion rate% | Selectivity% |
| Example 11 | 120 | 55.29 | 87.44 |
| Example 12 | 130 | 70.36 | 89.19 |
| Example 13 | 150 | ≈100 | 81.63 |
Examples 14 to 16
1, 3-dihydroxyacetone was prepared in the same manner as in example 3, except that the solvents shown in Table 4 below were used, and the results of the experiments were as shown in Table 4.
TABLE 4
| Name of the embodiment | Kind of solvent | Conversion rate% | Selectivity% |
| Example 14 | Isopropanol (I-propanol) | ≈100 | 86.97 |
| Example 15 | N, N-dimethyl acetamide | ≈100 | 93.15 |
| Example 16 | Dimethyl sulfoxide | ≈100 | 82.06 |
Example 17
The catalyst described in example 3 was replaced by a conventional 3-ethylbenzothiazole bromide salt and triethylamine catalyst system under the same conditions as in example 3, and the results of the experiments are shown in Table 5.
| Name of the embodiment | Catalytic system | Conversion rate% | Selectivity% |
| Example 17 | Brominated 3-ethylbenzothiazole salt and triethylamine | ≈100 | 83.23 |
However, since the brominated 3-ethylbenzothiazole salt and the triethylamine catalyst system are both small molecules, subsequent catalyst recovery is difficult.
The invention adopts the immobilized catalyst, which is easy to recycle and has high activity, and the reaction for preparing the 1, 3-dihydroxyacetone has high conversion rate and high selectivity by using the catalyst.
Claims (10)
1. An immobilized carbene catalyst having the following structure:
wherein n is the polymerization degree of the polystyrene carrier, and is an integer of 100-10000,represents a silica carrier.
2. A method of preparing the immobilized carbene catalyst of claim 1, the method comprising the steps of:
a) selecting a chlorine ball with the crosslinking degree of 7 and the chlorine content of 12.8 percent as a carrier, swelling the carrier by using a mixed solvent of 1, 2-dichloroethane and ethanol for 8 to 16 hours, and then adding Cl: adding benzothiazole into benzothiazole with the mol ratio of N contained in the benzothiazole being 1:1, performing reflux reaction for 8-16 hours, performing suction filtration, washing, and extracting by using absolute ethyl alcohol to obtain quaternized polystyrene resin;
b) putting the quaternized polystyrene resin obtained in the step a) into a reaction kettle containing dioxane, adding triethylamine according to the molar ratio of Cl contained in chlorine spheres to N contained in triethylamine of 1:1, reacting for 16-28h at 373K under the protection of nitrogen, filtering under the protection of nitrogen, extracting with absolute ethyl alcohol, and drying in vacuum to obtain a polystyrene-immobilized carbene catalyst;
or,
a') mixing the silicon dioxide with excessive 20 wt% hydrochloric acid aqueous solution, stirring and reacting for 3-6h at 373K, filtering and drying to obtain activated silicon dioxide;
b ') mixing the activated silicon dioxide prepared in the step a') with anhydrous toluene and 3-bromopropyltrimethoxysilane, refluxing and reacting for 4-12h under stirring, filtering, washing with methanol, and drying in vacuum to obtain functionalized silicon dioxide;
c ') mixing the functionalized silica prepared in the step b') with anhydrous toluene, adding benzothiazole according to the molar ratio of Br contained in the functionalized silica to N contained in the benzothiazole of 1:1, refluxing and reacting for 18-30h under stirring, filtering, washing with methanol, and drying in vacuum to obtain silica-immobilized bromine salt;
d ') mixing the silica-supported bromine salt prepared in step c') with dioxane, and reacting the silica-supported bromine salt with a catalyst selected from the group consisting of Br: adding triethylamine into the triethylamine at a molar ratio of N to N of 1:1, stirring the mixture under the protection of nitrogen and 373K for reacting for 8-24h, then filtering under the protection of nitrogen, extracting with absolute ethyl alcohol, and drying in vacuum to obtain the silica-supported carbene catalyst.
3. A method of preparing 1, 3-dihydroxyacetone by catalyzing the condensation of formaldehyde using the immobilized carbene catalyst of claim 1, the method comprising the steps of:
adding paraformaldehyde, a solvent and the immobilized carbene catalyst into a reaction kettle respectively at room temperature, stirring, simultaneously heating to 100-150 ℃, and reacting for 0.5-5 h under the protection of nitrogen to prepare the 1, 3-dihydroxyacetone.
4. The method of claim 3, wherein the solvent is ethanol, isopropanol, 1, 4-dioxane, 1, 3-dioxolane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, or a mixture thereof.
5. The method of claim 4, wherein the solvent is isopropanol, N-dimethylacetamide, 1, 3-dioxolane, dimethylsulfoxide, or a mixture thereof.
6. The method according to any one of claims 3 to 5, wherein the amount of the solvent is 2 to 10 times the mass of paraformaldehyde.
7. The method according to any one of claims 3 to 5, wherein the amount of the immobilized carbene catalyst is 0.1-2 times of the mass of paraformaldehyde.
8. The method according to any one of claims 3 to 5, wherein the amount of the immobilized carbene catalyst is 0.1 to 0.4 times of the mass of paraformaldehyde.
9. The method according to any one of claims 3 to 5, wherein the amount of the immobilized carbene catalyst is 0.15 to 0.35 times of the mass of paraformaldehyde.
10. The process according to any one of claims 3 to 5, wherein the reaction time is 1 to 4 hours.
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