CN116283840A - Preparation method of high-yield four-membered ring beta-lactone compound - Google Patents
Preparation method of high-yield four-membered ring beta-lactone compound Download PDFInfo
- Publication number
- CN116283840A CN116283840A CN202310306822.1A CN202310306822A CN116283840A CN 116283840 A CN116283840 A CN 116283840A CN 202310306822 A CN202310306822 A CN 202310306822A CN 116283840 A CN116283840 A CN 116283840A
- Authority
- CN
- China
- Prior art keywords
- beta
- membered ring
- lactone compound
- yield
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 beta-lactone compound Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 19
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960000380 propiolactone Drugs 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000006227 byproduct Substances 0.000 claims abstract description 9
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical group [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 238000003303 reheating Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 239000011943 nanocatalyst Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DBXBTMSZEOQQDU-UHFFFAOYSA-N 3-hydroxyisobutyric acid Chemical compound OCC(C)C(O)=O DBXBTMSZEOQQDU-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 125000003180 beta-lactone group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
- C07D305/12—Beta-lactones
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of organic chemistry, in particular to a preparation method of a high-yield four-membered ring beta-lactone compound, which comprises the following steps: 3-hydroxy alkyl acid compound is used as raw material, and is added into evenly dispersed solvent containing catalyst, and the temperature is raised to carry out dehydration cyclization reaction and evaporate out the produced by-product water; under the protection of nitrogen, heating again, and distilling to obtain a product four-ring beta-lactone compound; the catalyst is nano silicon dioxide and/or aluminum oxide; the four-membered ring beta-lactone compound is beta-propiolactone or beta-butyrolactone. The method has the advantages of stable and easily available raw materials, low cost, simple preparation process and high yield of the composite catalyst product of more than 88 weight percent; the single catalyst has the product yield of more than 72 weight percent and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of organic chemistry, in particular to a preparation method of a high-yield four-membered ring beta-lactone compound.
Background
The organic heterocyclic small molecular lactone is a complex molecular raw material for synthesizing biodegradable polymers and the like, and a large amount of lactone compounds are synthesized and continuously participate in the reaction as reaction intermediates in the fields of material science and organic synthesis. Generally, lactone compounds are obtainable from the cycloaddition of an ketene compound and a carbon-oxygen bond containing compound.
Beta-propiolactone can be prepared by cyclizing addition reaction of ketene and formaldehyde in anhydrous medium in the presence of zinc chloride or in the presence of boric acid catalyst, however, the ketene has higher reactivity, is very unstable at normal temperature, can be stored only at low temperature, and can undergo polymerization reaction at 0 ℃ to generate dimer diketene, so that the ketene needs to be prepared in situ, the condition is harsh, and the preparation process is complicated.
Disclosure of Invention
Aiming at the technical problems that the raw materials are easy to deteriorate, the preparation process is complex and difficult to prepare in the preparation process of propiolactone with a four-membered ring and large intramolecular tension in the molecular structure, the preparation method of the four-membered ring beta-lactone with high yield is provided. The method is efficient and green, can prepare the four-membered ring beta-lactone compound with a high yield of more than 72wt%, has the advantages of easily available raw materials, low cost and simple preparation process, and is suitable for industrial production.
In order to achieve the above object. The invention is realized by the following technical scheme:
the preparation method of the four-membered ring beta-lactone compound with high yield comprises the following steps:
3-hydroxy alkyl acid compound is used as raw material, and is added into evenly dispersed solvent containing catalyst, and the temperature is raised to carry out dehydration cyclization reaction and evaporate out the produced by-product water; under the protection of nitrogen, heating again, and distilling to obtain a product four-ring beta-lactone compound;
the structural formula of the 3-hydroxy alkyl acid compound is as follows:
the catalyst is nano silicon dioxide and/or aluminum oxide;
the four-membered ring beta-lactone compound is beta-propiolactone (boiling point 162 ℃) or beta-butyrolactone (boiling point 163.2 ℃).
Further, the particle size of the nano silicon dioxide is 10-50nm, and the specific surface area is more than 200m 2 /g; the alumina is beta-Al 2 O 3 Particle diameter of 10-50nm and specific surface area of 230m or more 2 /g; the solvent is an organic solvent with a boiling point greater than that of the four-membered ring beta-lactone compound, and is not miscible with water.
Preferably, the solvent is cyclohexylbenzene (boiling point 238-240 ℃).
Further, the uniformly dispersed catalyst-containing solvent and the 3-hydroxyalkylacid compound are required to be heated to 60-80 ℃ in advance, respectively, and the temperature difference between the two is not more than + -2 ℃; the addition time of the 3-hydroxyalkanoic acid compound per mole is controlled within 12-18 min.
Further, the temperature of the dehydrative ring closure reaction is set to be at least 25 ℃ below the boiling point of the four-membered ring beta-lactone compound and the reaction temperature is higher than 100 ℃; preferably, the temperature of the dehydrative ring closure reaction is 125-135 ℃.
Further, when the mole number of the byproduct water produced by the distillation is 80% or more of the mole number of the 3-hydroxyalkylacid compound, the nitrogen gas is started to be introduced and the temperature is raised. Namely, when the dehydration cyclization reaction progress reaches more than 80%, the temperature is raised to evaporate the product.
Further, the temperature of the mixture is set to be 5-15 ℃ higher than the boiling point of the four-membered ring beta-lactone compound; the temperature rising rate of the secondary temperature rising is 0.8-1.2 ℃/min.
Further, the ratio of the amount of the 3-hydroxyalkylacid compound to the amount of the solvent is 1mol (400-800) mL; the catalyst is used in an amount of 0.8g/mol to 2g/mol relative to the 3-hydroxyalkylacid compound.
The beneficial technical effects are as follows:
according to the invention, a 3-hydroxy alkyl acid compound (3-hydroxy propionic acid or 3-hydroxy isobutyric acid) is used as a raw material, nano silicon dioxide and/or beta-alumina are used as catalysts, and the specific surface area of the nano catalyst is large, so that the 3-hydroxy alkyl acid compound is adsorbed by the nano catalyst, the surface of the nano catalyst has stronger acid sites and certain surface alkalinity, and intramolecular dehydration cyclization is carried out under the action of the nano catalyst to form a product tetra-ring beta-lactone (beta-propiolactone or beta-butyrolactone);
the nano catalyst adopted by the invention has stable property, can be repeatedly used for more than 4 times, and needs to be added with 10% of the amount to supplement the physical loss in the synthesis process when in fifth use; during the dehydration reaction, the byproduct water generated can be distilled out through a Kelvin distillation head, so that the dehydration reaction can be completely carried out, after the dehydration reaction process reaches more than 80%, nitrogen is introduced to remove the byproduct water, and then the temperature is raised to distill out the product and collect the obtained product;
the raw materials used in the method have stable and easily available properties, low cost and simple preparation process, and are suitable for industrial production; the method of the invention takes 3-hydroxy alkyl acid compound as raw material and nano silicon dioxide and/or beta-alumina as catalyst to carry out intramolecular dehydration cyclization to obtain corresponding four-membered ring beta-lactone, and the yield of the composite catalyst product is more than 88 wt%; the yield of the single catalyst is above 72 wt%.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The numerical values set forth in these examples do not limit the scope of the present invention unless specifically stated otherwise. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods in the following examples, for which specific conditions are not noted, are generally determined according to national standards; if the national standard is not corresponding, the method is carried out according to the general international standard or the standard requirements set by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
The particle size of the nano silicon dioxide is 10-50nm, and the specific surface area is more than 200m 2 /g; the alumina used is beta-Al 2 O 3 Particle diameter of 10-50nm and specific surface area of 230m or more 2 /g。
Example 1
The preparation method of the beta-propiolactone comprises the following steps:
(1) Into a 1000mL four-necked flask equipped with mechanical stirring, thermometer, dropping tube and Kjeldahl distillation head, 600mL of cyclohexylbenzene was added, followed by 0.8g of SP15 nano SiO 2 And 0.5g of nanoscale beta-Al 2 O 3 Dispersing by high shear stirring, and heating to 75deg.C to obtain a standby liquid;
(2) Heating 90g (1 mol) of 3-hydroxy propionic acid to 75 ℃, and dropwise adding the 3-hydroxy propionic acid into the standby liquid in the step (1) for 15min under stirring to form a mixed liquid;
(3) Heating the mixed solution to 130 ℃ for dehydration cyclization reaction, carrying out heat preservation reaction at 130 ℃ and distilling out byproduct water, and when 15.5g of water is distilled out, changing a nitrogen inlet pipe of a dropping liquid pipe and introducing nitrogen;
under the protection of nitrogen, the mixture is heated to 172 ℃ in 45min, 66g of product is distilled off, and beta-propiolactone is obtained.
The purity of beta-propiolactone in the product of this example was 96.8wt%, and the beta-propiolactone was detected by nuclear magnetic resonance-hydrogen spectrometry 1 H NMR:δ3.55(t,2H),4.28(t,2H)。
The beta-propiolactone yield of this example was 88.7wt%.
Comparative example 1
The procedure of this comparative example was the same as in example 1, except that 0.8g of SP15 nano-SiO in example 1 was used 2 And 0.5g of nanoscale beta-Al 2 O 3 Replaced with 20g of HY molecular sieve.
The beta-propiolactone yield of this example was only 31.6wt%, and the beta-propiolactone was examined by nuclear magnetic resonance-hydrogen spectrometry 1 H NMR:δ3.55(t,2H),4.28(t,2H)。
Meanwhile, the comparative example also carries out reaction at 172 ℃ by taking 3-hydroxy propionic acid as a raw material under the condition of no catalyst, and the experiment shows that: the 3-hydroxy propionic acid can produce intermolecular polycondensation under the condition of no catalyst at high temperature to obtain polyester.
Example 2
The procedure of this example was the same as in example 1, except that 0.8g of SP15 nano-SiO in example 1 was used 2 And 0.5g of nanoscale beta-Al 2 O 3 Replaced by 1.5g of nano SiO 2 . I.e. only nano SiO is present in this embodiment 2 。
The beta-propiolactone yield of this example was 74.6wt%, and the beta-propiolactone was subjected to nuclear magnetic resonance-hydrogen spectrum detection 1 H NMR:δ3.55(t,2H),4.28(t,2H)。
Example 3
The procedure of this example was the same as in example 1, except that 0.8g of SP15 nano-SiO in example 1 was used 2 And 0.5g of nanoscale beta-Al 2 O 3 Replaced by 2g of nanoscale beta-Al 2 O 3 . I.e. only nanoscale beta-Al is present in this embodiment 2 O 3 。
The beta-propiolactone yield of this example was 72.4wt%, and the beta-propiolactone was subjected to nuclear magnetic resonance-hydrogen spectrum detection 1 H NMR:δ3.55(t,2H),4.28(t,2H)。
Example 4
SP15 nano SiO obtained by the primary synthesis in example 1 2 And nanoscale beta-Al 2 O 3 Filtering and recovering, and directly throwing into the Nth beta-propylThe lactone synthesis and product yield results are shown in Table 2.
TABLE 2 recycling efficiency of catalyst
The data show that the nano catalyst adopted by the invention has stable property, the yield of the product obtained by recycling for 4 times is not obviously reduced, and the yield of the product is reduced to below 80% in the fifth time if the product is directly recycled, so that the product is required to be respectively added with 10 weight percent to supplement the physical loss in the synthesis process in the fifth time of use, thereby achieving the purpose of high yield.
Example 5
The preparation method of the beta-butyrolactone comprises the following steps:
(1) Into a 1000mL four-necked flask equipped with a mechanical stirrer, a thermometer, a dropping tube and a Kjeldahl distillation head, 700mL of cyclohexylbenzene was added, followed by 0.1g of SP15 nano SiO 2 And 0.8g of nanoscale beta-Al 2 O 3 Dispersing by high shear stirring, and heating to 75deg.C to obtain a standby liquid;
(2) 104.1g (1 mol) of 3-hydroxyisobutyric acid is heated to 80 ℃, and 3-hydroxyisobutyric acid is added into the standby liquid in the step (1) dropwise under stirring for 15min to form a mixed liquid;
(3) Heating the mixed solution to 135 ℃ for dehydration cyclization reaction, preserving heat at 135 ℃ for reaction, distilling out byproduct water, and introducing nitrogen into a nitrogen inlet pipe of a dropping liquid pipe when 15.8g of water is distilled out;
under the protection of nitrogen, the mixture is heated to 175 ℃ in 48min, 78.9g of product is distilled off, and the purity content of the beta-butyrolactone in the product is 97.2wt%.
The yield of the beta-butyrolactone in the embodiment is 89.1wt percent, and nuclear magnetic resonance-hydrogen spectrum detection is carried out on the beta-butyrolactone 1 H NMR:δ3.37(t,2H),4.42(t,1H)，1.41(d,3H)。
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (9)
1. The preparation method of the four-membered ring beta-lactone compound with high yield is characterized by comprising the following steps:
3-hydroxy alkyl acid compound is used as raw material, and is added into evenly dispersed solvent containing catalyst, and the temperature is raised to carry out dehydration cyclization reaction and evaporate out the produced by-product water; under the protection of nitrogen, heating again, and distilling to obtain a product four-ring beta-lactone compound;
the structural formula of the 3-hydroxy alkyl acid compound is as follows:
the catalyst is nano silicon dioxide and/or aluminum oxide;
the four-membered ring beta-lactone compound is beta-propiolactone or beta-butyrolactone.
2. The method for producing a high-yield four-membered ring beta-lactone compound according to claim 1, wherein the nanosilica has a particle diameter of 10 to 50nm and a specific surface area of > 200m 2 /g; the alumina is beta-Al 2 O 3 Particle diameter of 10-50nm and specific surface area of 230m or more 2 /g; the solvent is an organic solvent with a boiling point greater than that of the four-membered ring beta-lactone compound, and is not miscible with water.
3. The method for producing a high-yield four-membered ring β -lactone compound according to claim 2, wherein the solvent is cyclohexylbenzene.
4. The method for producing a high-yield four-membered ring beta-lactone compound according to claim 1, wherein a solvent containing a catalyst and the 3-hydroxyalkylacid compound which are uniformly dispersed are required to be heated to 60 to 80 ℃ in advance, respectively, and the difference in temperature therebetween is not more than ±2 ℃; the addition time of the 3-hydroxyalkanoic acid compound per mole is controlled within 12-18 min.
5. The method for producing a high-yield four-membered ring β -lactone compound according to claim 1, wherein the temperature of the dehydrative ring closure reaction is set to be at least 25 ℃ lower than the boiling point of the four-membered ring β -lactone compound and the reaction temperature is higher than 100 ℃.
6. The method for producing a high-yield four-membered ring beta-lactone compound according to claim 5, wherein the temperature of the dehydrative ring closure reaction is 125 to 135 ℃.
7. The method for producing a four-membered ring beta-lactone compound according to claim 1, wherein the nitrogen gas is introduced and the temperature is raised when the number of moles of water as a by-product produced by the distillation is 80% or more of the number of moles of the 3-hydroxyalkylacid compound.
8. The method for producing a high-yield four-membered ring β -lactone compound according to claim 1, wherein the temperature of the reheating is set to 5 to 15 ℃ higher than the boiling point of the four-membered ring β -lactone compound; the temperature rising rate of the secondary temperature rising is 0.8-1.2 ℃/min.
9. The method for producing a high-yield four-membered ring β -lactone compound according to claim 1, wherein the ratio of the amount of said 3-hydroxyalkylacid compound to the amount of said solvent is 1mol (400-800) mL; the catalyst is used in an amount of 0.8g/mol to 2g/mol relative to the 3-hydroxyalkylacid compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310306822.1A CN116283840B (en) | 2023-03-27 | 2023-03-27 | Preparation method of high-yield four-membered ring beta-lactone compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310306822.1A CN116283840B (en) | 2023-03-27 | 2023-03-27 | Preparation method of high-yield four-membered ring beta-lactone compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116283840A true CN116283840A (en) | 2023-06-23 |
| CN116283840B CN116283840B (en) | 2024-05-14 |
Family
ID=86797626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310306822.1A Active CN116283840B (en) | 2023-03-27 | 2023-03-27 | Preparation method of high-yield four-membered ring beta-lactone compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116283840B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1140928A (en) * | 1967-11-29 | 1969-01-22 | Shell Int Research | Process for the preparation of -ß-lactones |
| US3915995A (en) * | 1972-11-03 | 1975-10-28 | Eastman Kodak Co | Production of 2,2-disubstituted propiolactones |
| US20120226055A1 (en) * | 2011-02-25 | 2012-09-06 | Massachusetts Institute Of Technology | Microbial production of 3,4-dihydroxybutyrate (3,4-dhba), 2,3- dihydroxybutyrate (2,3-dhba) and 3-hydroxybutyrolactone (3-hbl) |
| CN107365352A (en) * | 2017-07-26 | 2017-11-21 | 河南师范大学 | A kind of new tripeptide compound for containing 9 adenine alanine and its preparation method and application |
-
2023
- 2023-03-27 CN CN202310306822.1A patent/CN116283840B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1140928A (en) * | 1967-11-29 | 1969-01-22 | Shell Int Research | Process for the preparation of -ß-lactones |
| US3915995A (en) * | 1972-11-03 | 1975-10-28 | Eastman Kodak Co | Production of 2,2-disubstituted propiolactones |
| US20120226055A1 (en) * | 2011-02-25 | 2012-09-06 | Massachusetts Institute Of Technology | Microbial production of 3,4-dihydroxybutyrate (3,4-dhba), 2,3- dihydroxybutyrate (2,3-dhba) and 3-hydroxybutyrolactone (3-hbl) |
| CN107365352A (en) * | 2017-07-26 | 2017-11-21 | 河南师范大学 | A kind of new tripeptide compound for containing 9 adenine alanine and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| AUS DEM AMMONIAK-LABORATORIUM DER BADISCHEN ANILIN等: ""β-Lactone aus 3-Hydroxy-2.2-dialkyl-carbonsauren"", 《CHEM. BER.》, vol. 101, 31 December 1968 (1968-12-31), pages 2413 - 2418 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116283840B (en) | 2024-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111905828B (en) | Naphthyl ligand MOF activated carbon composite catalyst and preparation method and application thereof | |
| US9321744B1 (en) | Method for preparing 2,5-furan dicarboxylic acid | |
| TW201114751A (en) | Process for preparing glycidyl esters of branched monocarboxylic acids | |
| JP5395908B2 (en) | Process for producing 4- (1-hydroxy-1-methylethyl) -2-propylimidazole-5-carboxylic acid ester | |
| CN105622567A (en) | Preparation method of high-yield glycolide | |
| CN114315776B (en) | Method for preparing 2, 4-disubstituted tetrahydropyran compound through hydrogenolysis reaction | |
| CN111138423B (en) | Monomer of benzoxazine resin, benzoxazine resin and preparation method thereof | |
| JPH04225936A (en) | Process for producing 1,3-diketone | |
| CN116283840B (en) | Preparation method of high-yield four-membered ring beta-lactone compound | |
| CN114524823B (en) | Preparation method of tetracarboxylic dianhydride alicyclic compound | |
| KR101421514B1 (en) | Method for preparing isosorbide from sorbitol using water-compatible lewis acid | |
| CN109761947B (en) | Synthesis method of functionalized benzo chromene compound | |
| CN108003183B (en) | Method for catalyzing caprolactone polymerization by using tetradentate nitrogen-oxygen coordinated aluminum compound | |
| CN111393287A (en) | Novel process for synthesizing hexafluoroacetone | |
| TW202000636A (en) | Process for preparing bis(2-hydroxyethyl) terephthalate | |
| TW201120021A (en) | Process for preparing 2,4-dioxotetrahydrofuran-3-carboxylates | |
| CN109851518A (en) | The preparation method of the aceted intermediate of the fluoro- 3- methyl isobenzofuran -3- ketone of one kind (S) -5- | |
| CN111533698B (en) | 3-trifluoromethyl-5-aryl-1, 6-dihydropyridazine compound and preparation method thereof | |
| JPH0748454A (en) | Polysiloxane oligomer and production thereof | |
| CN114605234B (en) | Preparation method of trimethyl orthoacetate | |
| CN111875577B (en) | Preparation method of R-propylene carbonate | |
| CN107973906B (en) | Method for catalyzing lactide polymerization by using tetradentate nitrogen-oxygen coordinated aluminum compound | |
| CN116554196A (en) | Bio-based thermosetting epoxy resin curing agent and preparation method and application thereof | |
| CN114315577A (en) | Synthesis method of 2-ethoxymethylene-4, 4-difluoroacetoacetic acid ethyl ester | |
| CN117417239A (en) | Process for preparation of stearoyl benzoyl methane derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |